Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(22)
Published: Feb. 28, 2024
Abstract
The
solar‐driven
photocatalytic
production
of
hydrogen
peroxide
(H
2
O
)
from
water
and
oxygen
using
semiconductor
catalysts
offers
a
promising
approach
for
converting
solar
energy
into
storable
chemical
energy.
However,
the
efficiency
H
is
often
restricted
by
low
photo‐generated
charge
separation,
slow
surface
reactions
inadequate
stability.
Here,
we
developed
mixed‐linker
strategy
to
build
donor‐acceptor‐acceptor
(D–A–A)
type
covalent
organic
framework
(COF)
photocatalyst,
FS‐OHOMe‐COF.
FS‐OHOMe‐COF
structure
features
extended
π–π
conjugation
that
improves
mobility,
while
introduction
sulfone
units
not
only
as
active
sites
facilitates
with
but
also
bolsters
stability
through
increased
interlayer
forces.
resulting
has
exciton
binding
energy,
long
excited‐state
lifetime
high
photo‐stability
leads
performance
(up
1.0
mM
h
−1
an
output
19
after
72
hours
irradiation.
Furthermore,
catalyst
demonstrates
stability,
which
sustained
activity
over
192
experiment.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Nov. 6, 2023
Photocatalytic
two-electron
oxygen
reduction
to
produce
high-value
hydrogen
peroxide
(H2O2)
is
gaining
popularity
as
a
promising
avenue
of
research.
However,
structural
evolution
mechanisms
catalytically
active
sites
in
the
entire
photosynthetic
H2O2
system
remains
unclear
and
seriously
hinders
development
highly-active
stable
photocatalysts.
Herein,
we
report
high-loading
Ni
single-atom
photocatalyst
for
efficient
synthesis
pure
water,
achieving
an
apparent
quantum
yield
10.9%
at
420
nm
solar-to-chemical
conversion
efficiency
0.82%.
Importantly,
using
situ
synchrotron
X-ray
absorption
spectroscopy
Raman
directly
observe
that
initial
Ni-N3
dynamically
transform
into
high-valent
O1-Ni-N2
after
O2
adsorption
further
evolve
form
key
*OOH
intermediate
before
finally
forming
HOO-Ni-N2.
Theoretical
calculations
experiments
reveal
structure
reduces
formation
energy
barrier
suppresses
O=O
bond
dissociation,
leading
improved
production
activity
selectivity.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(5), P. 2975 - 2984
Published: Jan. 25, 2023
Multicomponent
reactions
(MCRs)
can
be
used
to
introduce
different
functionalities
into
highly
stable
covalent
organic
frameworks
(COFs).
In
this
work,
the
irreversible
three-component
Doebner
reaction
is
utilized
synthesize
four
chemically
quinoline-4-carboxylic
acid
DMCR-COFs
(DMCR-1-3
and
DMCR-1NH)
equipped
with
an
acid-base
bifunctionality.
These
show
superior
photocatalytic
H2O2
evolution
(one
of
most
important
industrial
oxidants)
compared
imine
COF
analogue
(Imine-1).
This
achieved
sacrificial
oxidants
but
also
in
pure
water
under
oxygen
or
air
atmosphere.
Furthermore,
high
photostability,
durability,
recyclability.
MCR-COFs
thus
provide
a
viable
materials'
platform
for
solar
chemical
energy
conversion.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
62(9)
Published: Dec. 30, 2022
The
full
reaction
photosynthesis
of
H2
O2
that
can
combine
water-oxidation
and
oxygen-reduction
without
sacrificial
agents
is
highly
demanded
to
maximize
the
light-utilization
overcome
complex
reaction-process
anthraquinone-oxidation.
Here,
a
kind
oxidation-reduction
molecular
junction
covalent-organic-framework
(TTF-BT-COF)
has
been
synthesized
through
covalent-coupling
tetrathiafulvalene
(photo-oxidation
site)
benzothiazole
(photo-reduction
site),
which
presents
visible-light-adsorption
region,
effective
electron-hole
separation-efficiency
photo-redox
sites
enables
generation
.
Specifically,
record-high
yield
(TTF-BT-COF,
≈276
000
μM
h-1
g-1
)
for
achieved
among
porous
crystalline
photocatalysts.
This
first
work
design
COFs
,
might
extend
scope
in
production.
Chemistry of Materials,
Journal Year:
2022,
Volume and Issue:
34(11), P. 5232 - 5240
Published: May 16, 2022
Covalent
organic
frameworks
(COFs)
are
an
ideal
template
for
photocatalytic
H2O2
synthesis
because
of
the
tunable
chemical
structures
and
semiconductor
properties.
However,
photoactivity
COFs
is
still
under-improved
due
to
inefficient
intrinsic
charge
generation,
fast
recombination
photogenerated
charges,
limited
electron
transport
along
frameworks.
Herein,
spatially
separated
synergistic
triazine
acetylene
units
first
integrated
into
(EBA-COF
BTEA-COF)
production.
The
spatial
separation
cores
leads
efficient
suppressed
recombination,
C═C
linkage
facilitates
electrons
over
skeletons.
Both
experimental
computational
results
suggested
that
synergistically
promote
in
a
two-electron
pathway.
EBA-COF
showed
attractive
activity
with
production
rate
1830
μmol
h–1
gcat–1,
superior
most
other
COF-based
catalysts.
This
study
provides
method
designing
photocatalysts
active
sites
based
on
vinylene-linked
COFs.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
62(9)
Published: Dec. 28, 2022
Covalent
organic
frameworks
(COFs)
are
highly
desirable
for
achieving
high-efficiency
overall
photosynthesis
of
hydrogen
peroxide
(H2
O2
)
via
molecular
design.
However,
precise
construction
COFs
toward
photosynthetic
H2
remains
a
great
challenge.
Herein,
we
report
the
crystalline
s-heptazine-based
(HEP-TAPT-COF
and
HEP-TAPB-COF)
with
separated
redox
centers
efficient
production
from
pure
water.
The
spatially
orderly
active
sites
in
HEP-COFs
can
efficiently
promote
charge
separation
enhance
photocatalytic
production.
Compared
HEP-TAPB-COF,
HEP-TAPT-COF
exhibits
higher
efficiency
integrating
dual
reduction
s-heptazine
triazine
moieties.
Accordingly,
bearing
remarkable
solar-to-chemical
energy
0.65
%
high
apparent
quantum
15.35
at
420
nm,
surpassing
previously
reported
COF-based
photocatalysts.
Chemistry of Materials,
Journal Year:
2022,
Volume and Issue:
34(10), P. 4259 - 4273
Published: May 11, 2022
Harnessing
solar
energy
to
generate
hydrogen
peroxide
(H2O2)
from
H2O
and
O2
via
artificial
photosynthesis
is
an
attractive
route,
as
this
approach
only
uses
sunlight
the
input.
Organic
polymers
have
emerged
a
promising
class
of
materials
for
solar-driven
H2O2
production,
owing
their
virtually
unlimited
molecular
building
blocks
rich
bond-forming
reactions.
This
distinctive
feature
leads
existence
different
reaction
pathways
characterized
by
electron
transfer
numbers.
For
overall
H2O2,
reduction
oxidation
must
occur
concurrently.
Thus,
in-depth
insights
into
these
are
crucial
with
eventual
aim
steering
optimize
efficiency.
In
perspective,
we
primarily
focus
on
state-of-the-art
progress
in
developing
polymer
photocatalysts
coupling
We
also
present
key
challenges
opportunities
production
future.
offer
ample
molecular-level
design
space.
They
now
found
extensive
applications
photochemical
Therefore,
perspective
serves
guideline
designing
toward
sustainable
has
significant
implications
future
development
broad
area
solar-to-chemical
conversion
research.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(30), P. 16584 - 16596
Published: July 24, 2023
In
this
work,
we
have
fabricated
an
aryl
amino-substituted
graphitic
carbon
nitride
(g-C3N4)
catalyst
with
atomically
dispersed
Mn
capable
of
generating
hydrogen
peroxide
(H2O2)
directly
from
seawater.
This
new
exhibited
excellent
reactivity,
obtaining
up
to
2230
μM
H2O2
in
7
h
alkaline
water
and
1800
seawater
under
identical
conditions.
More
importantly,
the
was
quickly
recovered
for
subsequent
reuse
without
appreciable
loss
performance.
Interestingly,
unlike
usual
two-electron
oxygen
reduction
reaction
pathway,
generation
through
a
less
common
oxidation
(WOR)
process
which
both
direct
indirect
WOR
processes
occurred;
namely,
photoinduced
h+
oxidized
H2O
via
one-step
2e-
WOR,
first
hydroxide
(OH-)
ion
generate
hydroxy
radical
(•OH),
formed
indirectly
by
combination
two
•OH.
We
characterized
material,
at
catalytic
sites,
atomic
level
using
electron
paramagnetic
resonance,
X-ray
absorption
near
edge
structure,
extended
fine
high-resolution
transmission
microscopy,
photoelectron
spectroscopy,
magic-angle
spinning
solid-state
NMR
multiscale
molecular
modeling,
combining
classical
reactive
dynamics
simulations
quantum
chemistry
calculations.
ACS ES&T Engineering,
Journal Year:
2022,
Volume and Issue:
2(6), P. 1068 - 1079
Published: Jan. 25, 2022
H2O2,
as
an
important
chemical
and
environmentally
friendly
oxidant,
has
been
applied
in
various
fields,
such
synthesis,
pulp
bleaching,
disinfection,
environmental
remediation.
Nevertheless,
the
industrial
anthraquinone
process
for
production
of
H2O2
is
energy-intensive
only
suitable
centralized
H2O2.
Photocatalytic
from
O2
reduction
a
promising
approach
on-site
decentralized
synthesis.
Although
photocatalysts
have
developed,
efficiency
still
limited
by
narrow
light
absorption
range,
rapid
charge
recombination,
slow
surface
reaction.
In
this
perspective,
we
briefly
introduce
basic
mechanism
photocatalytic
reduction.
Subsequently,
propose
design
principles
discuss
universal
strategies
enhancing
performance
production,
aspects
absorption,
separation,
catalytic
reaction,
reactor
configurations.
Finally,
present
our
prospects
suggestions
development
future.
We
hope
that
perspective
can
provide
useful
guidance
rational
efficient
novel
advance
both
insights
practical
applications
production.