ACS Applied Nano Materials,
Journal Year:
2022,
Volume and Issue:
5(5), P. 6055 - 6082
Published: April 15, 2022
Porphyrin-based
materials
are
excellent
chromophores
because
they
strongly
absorb
visible
light
and
their
relatively
low-energy
lowest
unoccupied
molecular
orbitals
thermodynamically
favor
photoinduced
electron
transfer.
They
can
generate
charge-transfer
excited
states
with
without
cocatalyst(s)
ease
energy
transfer
ultrafast
excitation
migration.
Combined
synthetic
accessibility,
these
qualities
make
them
ideal
building
blocks
for
porous
metal–organic
framework
(MOF)-
covalent–organic
(COF)-based
photocatalysts
to
produce
solar
fuels.
This
review
first
describes
the
structures
of
most
common
porphyrinic
MOFs
COFs
excited-state
properties
semiconducting
behavior
as
well
that
derived
composites.
The
generally
accepted
mechanisms
formation
H2,
CH4
derivatives,
N2
then
reviewed,
followed
by
detailed
examples
nano-MOFs
nano-COFs
used
said
purpose:
characteristic
parameters
such
rates
production,
turnover
numbers
(TONs),
frequencies
(TOFs),
apparent
quantum
efficiencies
described
compared.
shows
porphyrin-based
efficient
solar-fuel-producing
photocatalysts,
characteristics
comparable
those
nonporphyrinic
MOF
COF
although,
on
some
occasions,
production
fall
short
record
values.
Conversely,
exhibit
greatest
TONs
TOFs
any
or
but
still
face
shortcomings
concerning
selectivity
in
many
possible
side
products.
Importantly,
while
best
rate
photoproduction
fuels
has
been
observed
from
nanoscale
there
seem
be
no
drastic
differences
(within
μmol–1
h–1
mmol
g–1
h–1)
between
microscale
heterogeneous
photocatalysts.
observation
suggests
more
active
sites
mostly
located
at
near
surface
particles.
Overall,
nanosized
show
rich
promising
photocatalytic
generating
have
room
improvement.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(34)
Published: April 24, 2023
Abstract
Intensifying
energy
crises
and
severe
environmental
issues
have
led
to
the
discovery
of
renewable
sources,
sustainable
conversion,
storage
technologies.
Photocatalysis
is
a
green
technology
that
converts
eco‐friendly
solar
into
high‐energy
chemicals.
Covalent
organic
frameworks
(COFs)
are
porous
materials
constructed
by
covalent
bonds
show
promising
potential
for
converting
chemicals
owing
their
pre‐designable
structures,
high
crystallinity,
porosity.
Herein,
we
highlight
recent
progress
in
synthesis
COF‐based
photocatalysts
applications
water
splitting,
CO
2
reduction,
H
O
production.
The
challenges
future
opportunities
rational
design
COFs
advanced
discussed.
This
Review
expected
promote
further
development
toward
photocatalysis.
Small Methods,
Journal Year:
2022,
Volume and Issue:
7(1)
Published: Dec. 1, 2022
Abstract
Metal–organic
frameworks
(MOFs)
represent
a
novel
class
of
crystalline
inorganic–organic
hybrid
materials
with
tunable
semiconducting
behavior.
MOFs
have
potential
for
application
in
photocatalysis
to
produce
sustainable
solar
fuels,
owing
their
unique
structural
advantages
(such
as
clarity
and
modifiability)
that
can
facilitate
deeper
understanding
the
structure–activity
relationship
photocatalysis.
This
review
takes
photocatalytic
active
sites
particular
perspective,
summarizing
progress
MOF‐based
fuel
production;
mainly
including
three
categories
solar‐chemical
conversions,
water
splitting
hydrogen
fuel,
carbon
dioxide
reduction
hydrocarbon
nitrogen
fixation
high‐energy
carriers
such
ammonia.
focuses
on
types
photocatalysts
discusses
enhanced
activity
based
well‐defined
structure
MOFs,
offering
deep
insights
into
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: March 18, 2023
The
reaction
efficiency
of
reactants
near
plasmonic
nanostructures
can
be
enhanced
significantly
because
effects.
Herein,
we
propose
that
the
catalytic
activity
molecular
catalysts
may
also
dramatically.
Based
on
this
proposal,
develop
a
highly
efficient
and
stable
photocatalytic
system
for
hydrogen
evolution
(HER)
by
compositing
catalyst
cobalt
porphyrin
together
with
gold
nanoparticles,
around
which
effects
localized
electromagnetic
field,
local
heating,
hot
carrier
excitation
exist.
After
optimization,
HER
rate
turn-over
frequency
(TOF)
reach
3.21
mol
g−1
h−1
4650
h−1,
respectively.
In
addition,
remains
after
45-hour
cycles,
is
catalytically
being
illuminated
two
weeks.
attributed
to
surface
plasmon
resonance,
particularly
plasmon-generated
carriers.
These
findings
pave
new
convenient
way
developing
plasmon-based
photocatalysts
high
stability.
under
illumination.
Here,
authors
show
Co
bound
Au
nanoparticles
effects,
yielding
generation
rate.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(45)
Published: Sept. 20, 2022
The
insufficient
charge
separation
and
sluggish
exciton
transport
severely
limit
the
utilization
of
polymeric
photocatalysts.
To
resolve
above
issues,
we
incorporate
bountiful
carboxyl
substituents
within
a
novel
benzodiimidazole
oligomer
assemble
it
into
crystalline
semiconductor.
photocatalyst
is
polar,
hydrophilic,
short-range
crystalline,
capable
both
hydrogen
oxygen
evolution.
introduction
side-groups
adds
asymmetry
to
local
structure
increases
built-in
electric
field.
Further,
accelerated
carrier
transfer
enabled
via
crystallinity.
superior
production
rates
18.63
2.87
mmol
g-1
h-1
represent
one
best
performances
ever
reported
among
dual-functional
Our
work
initiates
studies
on
high-performance
photocatalysts,
opening
new
frontier
produce
solar
fuel.
