Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(34), P. 14574 - 14587
Published: July 28, 2020
Semiconducting
polymers
are
versatile
materials
for
solar
energy
conversion
and
have
gained
popularity
as
photocatalysts
sunlight-driven
hydrogen
production.
Organic
often
contain
residual
metal
impurities
such
palladium
(Pd)
clusters
that
formed
during
the
polymerization
reaction,
there
is
increasing
evidence
a
catalytic
role
of
in
polymer
photocatalysts.
Using
transient
operando
optical
spectroscopy
on
nanoparticles
F8BT,
P3HT,
dibenzo[b,d]thiophene
sulfone
homopolymer
P10,
we
demonstrate
how
differences
time
scale
electron
transfer
to
Pd
translate
into
evolution
activity
optima
at
different
concentrations.
For
F8BT
with
common
concentrations
>1000
ppm
(>0.1
wt
%),
find
quench
photogenerated
excitons
via
femto-nanosecond
scale,
thus
outcompeting
reductive
quenching.
We
spectroscopically
identify
reduced
our
from
microsecond
onward
show
predominant
location
long-lived
electrons
gradually
shifts
when
content
lowered.
While
low
yield
limits
P10
exhibits
substantially
higher
activity,
which
results
yields
due
more
efficient
Surprisingly,
despite
performance
reside
rather
than
particles,
even
very
high
27000
(2.7
%).
In
contrast,
already
before
typical
evolution.
This
comparison
shows
quenching
but
slow
clusters,
whereas
opposite
case
F8BT.
These
findings
suggest
development
must
target
combine
both
rapid
charge
metal-based
cocatalyst.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(6), P. 2747 - 2754
Published: Feb. 2, 2022
Development
of
water-stable
metal-organic
frameworks
(MOFs)
for
promising
visible-light-driven
photocatalytic
water
splitting
is
highly
desirable
but
still
challenging.
Here
we
report
a
novel
p-type
nickel-based
MOF
single
crystal
(Ni-TBAPy-SC)
and
its
exfoliated
nanobelts
(Ni-TBAPy-NB)
that
can
bear
wide
range
pH
environment
in
aqueous
solution.
Both
experimental
theoretical
results
indicate
feasible
electron
transfer
from
the
H4TBAPy
ligand
(light-harvesting
center)
to
Ni-O
cluster
node
(catalytic
center),
on
which
produce
hydrogen
be
efficiently
driven
free
cocatalyst.
Compared
crystal,
two-dimensional
(2D)
show
more
efficient
charge
separation
due
shortened
distance
remarkably
enhanced
active
surface
areas,
resulting
164
times
promoted
reduction
activity.
The
optimal
H2
evolution
rate
nanobelt
reaches
98
μmol
h-1
(ca.
5
mmol
g-1)
showing
benchmarked
apparent
quantum
efficiency
(AQE)
8.0%
at
420
nm
among
MOFs
photocatalysts.
ACS Catalysis,
Journal Year:
2021,
Volume and Issue:
11(4), P. 2098 - 2107
Published: Feb. 2, 2021
Developing
photocatalysts
capable
of
visible-light-driven
water
splitting
to
produce
clean
hydrogen
(H2)
is
one
the
premier
challenges
for
solar
energy
conversion
into
and
sustainable
fuels.
Inspired
from
structure
feature
photosystem
I
in
nature,
we
have
designed
synthesized
a
series
robust
covalent
organic
frameworks
(NKCOFs
=
Nankai
University
COFs)
based
on
electric
donor–acceptor
moieties,
which
electron-donor
group
pyrene
can
be
used
harvesting
light.
Meanwhile,
benzothiadiazole
with
different
functional
groups
was
introduced
as
an
electron
acceptor
tune
light-adsorption
ability
COFs.
Notably,
activity
NKCOF-108
photochemical
H2
evolution
under
visible
light
among
highest
COFs
without
hybridization
other
materials.
We
attribute
high
rate
its
distinct
structural
features
wide
visible-light-response
range.
The
highly
ordered
layered
ensures
that
sufficient
active
sites
are
accessible
production,
design
promote
separation
photogenerated
carriers.
Our
findings
provided
effective
strategy
light-driven
evolution.
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
59(51), P. 22828 - 22839
Published: July 1, 2020
Abstract
Owing
to
the
intrinsically
low
dielectric
properties,
robust
Coulomb
interactions
between
photoinduced
electrons
and
holes
lead
dramatically
strong
exciton
effects
in
polymeric
photocatalysts.
Such
endow
matrixes
with
nontrivial
photoexcitation
processes
determining
photocatalytic
energy
utilization.
In
this
Minireview,
we
describe
recent
progress
investigation
of
excitonic
effect
On
basis
understanding
systems,
outline
relationships
behaviors
performance.
Advances
optimizing
for
gaining
high‐efficiency
polymer‐based
photocatalysis
are
summarized.
We
also
discuss
challenges
field
forecast
directions
future
research.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(34), P. 14574 - 14587
Published: July 28, 2020
Semiconducting
polymers
are
versatile
materials
for
solar
energy
conversion
and
have
gained
popularity
as
photocatalysts
sunlight-driven
hydrogen
production.
Organic
often
contain
residual
metal
impurities
such
palladium
(Pd)
clusters
that
formed
during
the
polymerization
reaction,
there
is
increasing
evidence
a
catalytic
role
of
in
polymer
photocatalysts.
Using
transient
operando
optical
spectroscopy
on
nanoparticles
F8BT,
P3HT,
dibenzo[b,d]thiophene
sulfone
homopolymer
P10,
we
demonstrate
how
differences
time
scale
electron
transfer
to
Pd
translate
into
evolution
activity
optima
at
different
concentrations.
For
F8BT
with
common
concentrations
>1000
ppm
(>0.1
wt
%),
find
quench
photogenerated
excitons
via
femto-nanosecond
scale,
thus
outcompeting
reductive
quenching.
We
spectroscopically
identify
reduced
our
from
microsecond
onward
show
predominant
location
long-lived
electrons
gradually
shifts
when
content
lowered.
While
low
yield
limits
P10
exhibits
substantially
higher
activity,
which
results
yields
due
more
efficient
Surprisingly,
despite
performance
reside
rather
than
particles,
even
very
high
27000
(2.7
%).
In
contrast,
already
before
typical
evolution.
This
comparison
shows
quenching
but
slow
clusters,
whereas
opposite
case
F8BT.
These
findings
suggest
development
must
target
combine
both
rapid
charge
metal-based
cocatalyst.
