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
Abstract
Covalent
organic
frameworks
(COFs),
known
for
the
precise
tunability
of
molecular
structures,
hold
significant
promise
photocatalytic
hydrogen
peroxide
(H
2
O
)
production.
Herein,
by
systematically
altering
quinoline
(QN)
linkages
in
triazine
(TA)‐based
COFs
via
multi‐component
reactions,
six
R‐QN‐TA‐COFs
are
synthesized
with
identical
skeletons
but
different
substituents.
The
fine‐tuning
optoelectronic
properties
and
local
microenvironment
is
allowed,
thereby
optimizing
charge
separation
improving
interactions
dissolved
oxygen.
Consequently,
MeO‐QN‐TA‐COF
customized
to
achieve
an
impressive
rate
H
production
up
7384
µmol
g⁻
1
h⁻
under
air
atmosphere
water
without
any
sacrificial
agents,
surpassing
most
reported
COF
photocatalysts.
Its
high
stability
demonstrated
through
five
consecutive
recycling
experiments
characterization
recovered
COF.
reaction
mechanism
further
investigated
using
a
suite
quenching
experiments,
situ
spectroscopic
analysis,
theoretical
calculations.
enhanced
over
2e⁻
oxygen
reduction
oxidation
pathways.
Overall,
crucial
role
linkage
modulation
design
solar‐driven
effective
Population
growth,
urbanization,
industrialization,
and
increased
socioeconomic
activities
have
escalated
carbon
dioxide
(CO2)
formation
concentration
in
the
atmosphere.
Increased
generation
release
of
CO2
into
atmosphere
exacerbates
global
warming
impedes
environmental
sustainability.
One
strategies
to
combat
unpleasant
impact
is
conversion
useful
products.
This
study
reviews
benefits,
drawbacks,
recommendations
for
effectively
utilizing
conventional,
hybrid,
novel
technologies
converting
energy
chemical
The
deficiencies
noticed
with
chemical,
thermal,
biological,
catalytic
(CTs)
necessitated
use
hybrid
such
as
biochemical,
electrochemical,
photocatalytic,
plasma
chemical.
posits
that
development
deployment
CTs
like
bio-electrochemical,
photo-electrochemical,
artificial
photosynthesis
will
advance
research
domain
revolutionize
product
formation.
transformation
renewable
fuels
methane,
syngas,
C2
products
methanol,
formic
acid,
dimethyl
carbonate,
oxygenates,
formaldehyde,
hydrocarbons
is,
eco-friendly,
reduces
air
pollution,
mitigates
climate
change,
supports
security,
provides
valuable
feedstocks
industries.
recommends
optimization
process
parameters
reactor
design
configurations,
funding,
provision
regulatory
framework
support,
partnerships
among
academia,
industry
players,
government
agencies
achieve
cost
reduction,
reduce
impacts,
drawbacks
associated
CTs.
Materials Horizons,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Metal-free
photocatalysts
derived
from
earth-abundant
elements
have
drawn
significant
attention
owing
to
their
ample
supply
for
potential
large-scale
applications.
However,
it
is
still
challenging
achieve
highly
efficient
photocatalytic
performance
sluggish
charge
separation
and
lack
of
active
catalytic
sites.
Herein,
we
designed
constructed
a
series
covalently
bonded
organic
semiconductors
enhance
water
splitting
phenol
degradation.
Experimental
theoretical
results
revealed
that
the
transfer
mechanism
transformed
type
II
in
physical
mixture
Z-scheme
composite,
resulting
interfacial
electric
field
formed
at
interface
between
β-ketoenamine-linked
covalent
framework
(TP-COF)
urea
linked
perylene
diimide
(PDI)
semiconductor
(UP)
by
amide
bonds.
The
route
not
only
improved
but
also
preserved
high
redox
ability
both
semiconductors.
Moreover,
more
sites
were
created
net
UP
TP-COFs
with
bonds,
contributing
performance.
As
result,
HER,
OER
degradation
rates
613.30
μmol
g-1
h-1,
1169.36
0.81
h-1
achieved,
respectively.
This
work
provides
new
strategy
develop
metal-free
simultaneously
efficiency
site
activity.
