Inorganic Chemistry,
Год журнала:
2024,
Номер
63(52), С. 24778 - 24786
Опубликована: Дек. 17, 2024
Reasonable
construction
of
atomically
accurate
photocatalysts
is
the
key
to
building
efficient
photocatalytic
systems.
Herein,
we
propose
a
collective
effects
strategy
that
enables
consolidation
both
cobalt
single
atoms
(CoSAs)
and
nickel
nanoparticles
(NiNPs)
in
hierarchical
porous
MOFs
for
foundational
features
preparation
high-performance
photocatalysts.
Among
them,
optimal
sample
CoSAs/Al-bpydc/NiNPs
achieved
CO
generation
rate
12.8
mmol·g–1·h–1
selectivity
91%
4
h.
According
experiment
characterizations
theoretical
simulations,
found
CoSAs
facilitate
CO2
adsorption
activation,
while
NiNPs
promote
hydrogen
spillover
transfer
protons
CoSAs,
highlighting
effect
catalytic
system
with
multiple
active
sites.
Most
importantly,
as
proof
concept,
this
performance
enhancement
can
also
be
applied
other
hierarchically
MOF
photocatalysts,
such
Al-bpdc,
DUT-4,
UiO-67.
This
work
provides
new
insight
into
development
optimization
conversion
through
ingenious
design
Advanced Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 13, 2025
Abstract
Atomically
precise
copper
clusters
are
desirable
as
catalysts
for
elaborating
the
structure–activity
relationships.
The
challenge,
however,
lies
in
their
tendency
to
sinter
when
protective
ligands
removed,
resulting
destruction
of
structural
integrity
model
system.
Herein,
a
copper‐sulfur‐nitrogen
cluster
[Cu
8
(S
t
Bu)
4
(PymS)
]
(denoted
Cu
SN
)
is
synthesized
by
using
mixed
ligand
approach
with
strong
chelating
2‐mercaptopyrimidine
(PymSH)
and
relatively
weak
monodentate
tert‐butyl
mercaptan
ligands.
A
thermal‐resection
strategy
applied
selectively
peel
only
targeted
off,
which
induces
transformation
initial
into
new
more
stable
Cu–S–N
(S)
2
SN‐T
).
residual
bridging
S
2−
within
metal
core
forms
asymmetric
Cu‐S
species
near‐infrared
(NIR)
response,
endows
capability
full‐spectrum
responsive
CO
photoreduction,
achieving
≈100%
‐to‐CO
selectivity.
Especially
NIR‐driven
reduction,
it
has
evolution
42.5
µmol
g
−1
under
λ
>
780
nm.
Importantly,
this
work
represents
first
NIR
light‐responsive
efficient
photoreduction
opens
an
avenue
manipulation
structures
via
novel
thermolysis
develop
unprecedented
functionalized
materials.
Chemistry - An Asian Journal,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 16, 2025
Abstract
Photocatalytic
reduction
of
carbon
dioxide
(CO
2
)
realizes
the
recycling
emissions
and
storage
solar
energy
into
bonding
organics
at
same
time,
thus
attract
great
interest
in
field
environment.
However,
current
photocatalytic
performance
CO
cannot
match
industrial
application.
The
design
highly
efficient
photocatalysts
with
precise
selectivity
reliable
long‐term
stability
is
still
a
big
challenge,
partially
because
mechanism
to
guide
fabrication,
not
completely
clear
yet.
can
involve
most
eight
electrons
for
each
molecule,
during
which
several
pathways
might
be
opened
up
active
sites
consume
photocarriers
influence
stability.
are
dependent
on
electronic
structure
property
sites,
optimized
if
those
thermodynamically
or
kinetically
compatible
target
production.
This
review
will
summarize
strategy
designing
surface
investigation
relation
between
reduction,
looking
ahead
future
development
devices
reduction.
Advanced Functional Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 5, 2025
Abstract
Covalent–organic
frameworks
(COFs)
based
heterojunctions
photocatalytic
have
showed
great
potential
for
CO
2
upcycling.
Currently,
significant
progress
has
been
made
in
developing
such
photocatalysts,
yet
a
comprehensive
understanding
of
this
field
remains
lacking.
This
review
systematically
explores
the
inherent
relationship
between
COF‐based
heterojunction
innovations
and
CO₂
reduction,
aiming
to
establish
structure–performance–mechanism
correlation
that
guides
design
high‐efficiency
catalysts.
First,
fundamentals,
mechanisms,
related
principles
conversion,
as
well
advantages
COFs
application,
are
thoroughly
introduced.
Then,
state‐of‐the‐art
applied
reduction
discussed
from
following
critical
aspects:
interfacial
engineering,
spatial
charge
transfer
regulation,
active
component
hybridization,
half‐reaction
kinetic
optimization,
sites
engineering.
Subsequently,
systematic
overview
characterization
techniques
research
methodologies
probing
catalyst
structures
in‐depth
reaction
mechanisms
is
outlined.
Finally,
challenges
further
development
direction
proposed.
It
expected
can
provide
powerful
guidance
reference
toward
exploiting
high‐performance
photocatalysts
conversion.
Abstract
Maximizing
the
atom
efficiency
of
noble
metal
species
is
crucial
for
their
application,
but
directly
reducing
size
down
to
single
atoms
(SAs)
limited
when
facing
complex
situations
requiring
simultaneous
adsorption
and
activation
multiple
reactants.
Herein,
Schiff
base
condensation
1,3,5‐tris(4‐aminophenyl)benzene
2,5‐dibromoterephthalaldehyde
offered
a
Br‐tethered
covalent
organic
framework
(COF)
TAPB‐DBDH
co‐loading
ruthenium
(Ru)
SAs
nanoparticles
(NPs).
We
demonstrated
triadic
synergism
Ru
(Ru–C
3
N
1
),
NPs,
in
reductive
aminations
carbonyl
compounds
with
ammonia
hydrogen
primary
amines,
showing
high
yield,
large
turnover
number,
frequency,
stable
recycling,
broad
substrate
compatibility.
A
systematic
theoretic
experimental
study
revealed
that
cooperation
provided
strong
affinity
toward
compound
imine
intermediate
promote
conversion,
while
co‐existed
NPs
lowered
energy
barrier
H
2
cleavage.
Advanced Functional Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 16, 2025
Abstract
Covalent
organic
frameworks
(COFs)
metallization
offers
a
potent
protocol
for
augmenting
the
efficacy
of
artificial
photosynthesis
H
2
O
.
However,
hurdles
like
intractable
short
exciton
lifetime
and
precarious
metal
coordination
metallo‐COFs
impede
their
photocatalytic
proficiency.
Herein,
facile
universal
single‐atom
encapsulation
strategy
is
proposed,
through
which
Fe
atoms
are
precisely
anchored
in
pincer
structure
to
achieve
planar
locking
PP‐COF
enhance
its
π‐conjugation
effect.
The
Fe/PP‐COF
with
extremely
high
stability
exhibits
remarkable
migration
distance
(6.48–53.20
nm)
(296.75
ps),
representing
state‐of‐the‐art
COF
hitherto.
In
brand‐new
biphasic
flow
reactor,
within
60
h
reaction
allows
continuous
at
rate
1556
µmol
−1
an
unprecedented
concentration
100
m
,
no
leakage.
This
work
valuable
insights
into
developing
COFs
precise
regulation
single‐atoms
space‐time
production.
Catalysts,
Год журнала:
2025,
Номер
15(6), С. 562 - 562
Опубликована: Июнь 5, 2025
Covalent
triazine
frameworks
(CTFs)
are
a
class
of
porous
organic
semiconductors
containing
large
number
units,
which
gives
them
many
properties
suitable
for
photocatalysis,
such
as
high
porosity,
good
tunability,
and
excellent
chemical
stability.
However,
it
is
difficult
to
achieve
activity,
stability,
selectivity
at
the
same
time
using
single
CTF
in
specific
catalytic
reaction.
Therefore,
necessary
find
ways
combine
CTFs
with
other
materials
improve
their
photocatalysis
activity.
From
this
perspective,
some
construction
methods
latest
progress
CTF-based
composites
presented,
applications
field
introduced.
Finally,
future
proposed,
provides
insights
into
research
exploration
composites.
