Advanced Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 18, 2025
Abstract
Cyano‐functionalized
sp
2
‐carbon‐conjugated
covalent
organic
frameworks
(CN‐COFs)
have
been
considered
as
promising
candidates
for
artificial
photosynthesis
of
hydrogen
peroxide
(H
O
).
Nevertheless,
the
performance
CN‐COFs
is
inherently
limited
by
constrained
oxygen
capture
capacity,
insufficient
charge
separation,
and
rapid
carrier
recombination.
Herein,
study
rationally
reports
a
strategy
integrating
amidoxime
groups
(AO)
into
COF
through
one‐step
cyano
hydrolysis
process
to
increase
photocatalytic
H
production.
Combined
simulations
characterizations
reveal
that
introducing
AO
enhances
hydrophilicity,
stabilizes
adsorbed
Oxygen
(O
)
via
bonding,
accelerates
separation
transfer,
well
lowers
energy
barrier
reduction
reaction
pathway,
thus
achieving
an
unmatched
production
rate
6024
µmol
h
−1
g
.
Importantly,
solar‐to‐chemical
conversion
(SCC)
efficiency
PTTN‐AO
reaches
0.61%,
significantly
surpassing
natural
plants
(≈0.1%)
most
COF‐based
photocatalysts.
The
current
findings
are
encouraging
molecular
design
polymers
green
efficient
ACS Applied Materials & Interfaces,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 15, 2025
As
an
efficient,
sustainable,
and
environmentally
friendly
semiconductor
material,
covalent
organic
frameworks
(COFs)
can
generate
hydrogen
peroxide
(H2O2)
by
photocatalysis,
attracting
wide
attention
in
recent
years.
Herein,
the
effects
of
hydroxyl,
methoxyl,
vinyl
groups
imide-linked
two-dimensional
(2D)
COFs
on
photocatalytic
production
H2O2
were
studied
theoretically
experimentally.
The
introduction
greatly
promotes
photogenerated
charge
separation
migration
COFs,
providing
more
oxygen
adsorption
sites,
stronger
proton
affinity,
lower
intermediate
binding
energy,
which
effectively
facilitates
rapid
conversion
to
H2O2.
Further,
we
have
integrated
properties
situ
generation
continuous
consumption
unspecific
peroxygenases
(UPOs)
construct
a
mild
simple
photoenzyme
coupling
system
that
achieve
selective
activation
C–H
bonds
without
need
any
external
oxidants
or
sacrificial
agents.
This
simple,
stable,
compatible
avoids
irreversible
enzyme
damage
caused
excessive
exogenous
utilization
agents,
thus
efficient
green
pathway
for
fine
chemical
synthesis.
not
only
breaks
restriction
supplementation
UPO
catalytic
but
also
provides
new
practical
application
direction
production.
Efficient
sacrificial-agent-free
photosynthesis
of
H2O2
from
air
and
water
represents
the
greenest,
lowest-cost,
most
real-time
avenue
for
production
but
remains
a
challenging
issue.
Here,
we
show
general
effective
approach
through
structural
design
on
covalent
organic
frameworks
(COFs)
with
asymmetric
dual-function
hybrid
linkages
boosting
COFs.
Through
such
can
equip
COF
not
only
catalytic
active
center
also
special
function
isolating
D–A
motif,
which
consequently
endows
(CI-COF)
built
significantly
enhanced
efficiency
in
generation,
transmission,
separation
photogenerated
carriers,
relative
to
(II-COF
CC-COF)
symmetric
single-function
single
linkages.
Correspondingly,
performance
is
by
three
or
five
times.
Accompanied
largely
promoted
O2
utilization
conversion
36.6%
99.9%.
A
rare
dual-channel
suggested
CI-COF.
Advanced Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 18, 2025
Abstract
Cyano‐functionalized
sp
2
‐carbon‐conjugated
covalent
organic
frameworks
(CN‐COFs)
have
been
considered
as
promising
candidates
for
artificial
photosynthesis
of
hydrogen
peroxide
(H
O
).
Nevertheless,
the
performance
CN‐COFs
is
inherently
limited
by
constrained
oxygen
capture
capacity,
insufficient
charge
separation,
and
rapid
carrier
recombination.
Herein,
study
rationally
reports
a
strategy
integrating
amidoxime
groups
(AO)
into
COF
through
one‐step
cyano
hydrolysis
process
to
increase
photocatalytic
H
production.
Combined
simulations
characterizations
reveal
that
introducing
AO
enhances
hydrophilicity,
stabilizes
adsorbed
Oxygen
(O
)
via
bonding,
accelerates
separation
transfer,
well
lowers
energy
barrier
reduction
reaction
pathway,
thus
achieving
an
unmatched
production
rate
6024
µmol
h
−1
g
.
Importantly,
solar‐to‐chemical
conversion
(SCC)
efficiency
PTTN‐AO
reaches
0.61%,
significantly
surpassing
natural
plants
(≈0.1%)
most
COF‐based
photocatalysts.
The
current
findings
are
encouraging
molecular
design
polymers
green
efficient
