Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(24)
Опубликована: Март 31, 2022
Integrating
molecular
catalysts
into
designed
frameworks
often
enables
improved
catalysis.
Compared
with
porphyrin-based
frameworks,
metal-corrole-based
have
been
rarely
developed,
although
monomeric
metal
corroles
are
usually
more
efficient
than
porphyrin
counterparts
for
the
electrocatalytic
oxygen
reduction
reaction
(ORR)
and
evolution
(OER).
We
herein
report
on
porous
organic
polymers
(POPs)
as
ORR
OER
electrocatalysts.
M-POPs
(M=Mn,
Fe,
Co,
Cu)
were
synthesized
by
coupling
10-phenyl-5,15-(4-iodophenyl)corrole
tetrakis(4-ethynylphenyl)methane.
corrole
monomers,
displayed
significantly
enhanced
catalytic
activity
stability.
Co-POP
outperformed
other
achieving
four-electron
a
half-wave
potential
of
0.87
V
vs.
RHE
reaching
10
mA
cm-2
current
density
at
340
mV
overpotential.
This
work
is
unparalleled
to
develop
explore
POPs
Advanced Materials,
Год журнала:
2021,
Номер
33(33)
Опубликована: Июль 8, 2021
Abstract
The
precise
identification
of
single‐atom
catalysts
(SACs)
activity
and
boosting
their
efficiency
toward
CO
2
conversion
is
imperative
yet
quite
challenging.
Herein,
for
the
first
time
a
series
porous
organic
polymers
designed
prepared
simultaneously,
containing
well‐defined
M–N
4
O
sites.
Such
strategy
not
only
offers
multiactive
sites
to
promote
catalytic
but
also
provides
more
direct
chance
identify
metal
center
activity.
photoreduction
results
indicate
that
introduction
salphen
unit
with
Ni–N
centers
into
pristine
phthalocyanine‐based
framework
achieves
remarkable
generation
ability
(7.77
mmol
g
–1
)
high
selectivity
96%
over
H
.
In
combination
control
experiments,
as
well
theoretical
studies,
moiety
evidenced
active
site
RR
compared
traditional
moiety,
which
can
be
ascribed
effectively
reducing
energy
barrier,
facilitating
adsorption
reaction
radicals
*COOH,
improving
charge
transportation.
This
work
might
shed
some
light
on
designing
efficient
SACs
reduction
through
modification
coordination
environments.
Nano Letters,
Год журнала:
2022,
Номер
22(6), С. 2529 - 2537
Опубликована: Март 10, 2022
Electrochemically
converting
nitrate
to
ammonia
is
a
promising
route
realize
artificial
nitrogen
recycling.
However,
developing
highly
efficient
electrocatalysts
an
ongoing
challenge.
Herein,
we
report
the
construction
of
stable
and
redox-active
zirconium
metal-organic
frameworks
(Zr-MOFs)
based
on
Zr6
nanoclusters
redox-reversible
tetrathiafulvalene
(TTF)
derivatives
as
inorganic
nodes
organic
linkers,
respectively.
The
Zr-MOF
can
facilitate
in
situ
reduction
noble
metal
precursors
free
external
reductants
uniform
nucleation
nanodots
(NDs)
Zr-MOF,
achieving
preparation
M-NDs/Zr-MOF
(M
=
Pd,
Ag,
or
Au).
porous
with
good
conductivity
mass
transfer
process.
Among
catalysts,
Pd-NDs/Zr-MOF
exhibits
highest
electrocatalytic
activity,
delivering
NH3
yield
287.31
mmol·h-1·g-1cat.
Faradaic
efficiency
58.1%.
proposed
interfacial
strategy
for
anchoring
M
NDs
Zr-MOFs
be
applied
other
challenging
energy
conversion
reactions.
Charge
separation
efficiency
of
photocatalysts
is
still
the
key
scientific
issue
for
solar-to-chemical
energy
conversion.
In
this
work,
an
electron
donor-acceptor
(D-A)
interface
with
high
charge
between
TPPS
(tetra(4-sulfonatophenyl)porphyrin)
and
PDI
(perylene
diimide)
successfully
constructed
boosting
photocatalytic
H
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Июнь 26, 2023
To
achieve
high-efficiency
catalysts
for
CO2
reduction
reaction,
various
catalytic
metal
centres
and
linker
molecules
have
been
assembled
into
covalent
organic
frameworks.
The
amine-linkages
enhance
the
binding
ability
of
molecules,
ionic
frameworks
enable
to
improve
electronic
conductivity
charge
transfer
along
However,
directly
synthesis
with
is
hardly
achieved
due
electrostatic
repulsion
predicament
strength
linkage.
Herein,
we
demonstrate
reaction
by
modulating
linkers
linkages
template
framework
build
correlation
between
performance
structures
Through
double
modifications,
states
are
well
tuned,
resulting
in
controllable
activity
selectivity
reaction.
Notably,
dual-functional
achieves
high
a
maximum
CO
Faradaic
efficiency
97.32%
turnover
frequencies
value
9922.68
h-1,
which
higher
than
those
base
single-modified
Moreover,
theoretical
calculations
further
reveal
that
attributed
easier
formation
immediate
*CO
from
COOH*.
This
study
provides
insights
developing
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
61(5)
Опубликована: Ноя. 22, 2021
Strategies
that
enable
simultaneous
morphology-tuning
and
electroreduction
performance
boosting
are
much
desired
for
the
exploration
of
covalent
organic
frameworks
in
efficient
CO2
electroreduction.
Herein,
a
kind
functionalizing
exfoliation
agent
has
been
selected
to
simultaneously
modify
exfoliate
bulk
COFs
into
functional
nanosheets
investigate
their
performance.
The
obtained
(Cu-Tph-COF-Dct)
with
large-scale
(≈1.0
μm)
ultrathin
(≈3.8
nm)
morphology
superior
FECH4
(≈80
%)
(almost
doubly
enhanced
than
bare
COF)
large
current-density
(-220.0
mA
cm-2
)
at
-0.9
V.
boosted
can
be
ascribed
immobilized
(Dct
groups)
integrated
amino
triazine
groups
strengthen
absorption/activation,
stabilize
intermediates
enrich
CO
concentration
around
Cu
active
sites
as
revealed
by
DFT
calculations.
point-to-point
functionalization
strategy
modularly
assembling
Dct-functionalized
COF
catalyst
will
open
up
attractive
possibility
developing
RR
electrocatalysts.
Advanced Functional Materials,
Год журнала:
2022,
Номер
32(23)
Опубликована: Март 4, 2022
Abstract
Metal–nitrogen–carbon
(M–N–C)
materials
have
attracted
much
interest
in
bifunctional
oxygen‐involving
electrocatalysis
for
rechargeable
Zn–air
batteries.
Such
M–N–C
electrocatalysts
with
M–N
x
sites
show
good
activity
the
oxygen
reduction
reaction
(ORR)
but
moderate
evolution
(OER).
Herein,
an
oxygen‐rich
material
(O–Co–N/C)
a
highly
porous
nanosheet
structure
is
reported
as
electrocatalyst,
which
prepared
by
direct
pyrolysis
of
ultrathin
CoO
nanosheets
decorated
zeolitic
imidazolate
framework‐8
nanoparticles
under
inert
atmosphere.
Particularly,
Co
O–Co–N/C
electrocatalyst
contain
both
Co–N
and
Co–O
coordination
environments
to
provide
intrinsic
active
ORR
OER,
respectively.
Furthermore,
electrochemical
studies
that
catalyst
retains
comparable
common
half‐wave
potential
0.85
V
vs
reversible
hydrogen
electrode
better
OER
overpotential
0.29
at
current
density
10
mA
cm
−2
.
This
study
provides
insights
into
development
effective
metal
centers
coordinated
nitrogen
atoms.
Advanced Materials,
Год журнала:
2021,
Номер
33(52)
Опубликована: Окт. 8, 2021
Covalent
organic
frameworks
(COFs)
are
a
class
of
porous
crystalline
materials
whose
facile
preparation,
functionality,
and
modularity
have
led
to
their
becoming
powerful
platforms
for
the
development
molecular
devices
in
many
fields
(bio)engineering,
such
as
energy
storage,
environmental
remediation,
drug
delivery,
catalysis.
In
particular,
ionic
COFs
(iCOFs)
highly
useful
constructing
devices,
functional
groups
can
transport
ions
efficiently,
nonlabile
ordered
all-covalent
pore
structures
backbones
provide
ideal
pathways
long-term
under
harsh
electrochemical
conditions.
Here,
current
research
progress
on
use
iCOFs
specifically
lithium-based
batteries
fuel
cells,
is
reviewed
terms
iCOF
backbone-design
strategies,
synthetic
approaches,
properties,
engineering
techniques,
applications.
categorized
anionic
or
cationic
COFs,
how
each
these
types
lithium
ions,
protons,
hydroxides
illustrated.
Finally,
challenges
future
opportunities
utilization
described.
This
review
will
therefore
serve
reference
state-of-the-art
design
application
strategies
focusing
devices.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
61(1)
Опубликована: Окт. 30, 2021
Synthesis
of
functional
3D
COFs
with
irreversible
bond
is
challenging.
Herein,
imide-bonded
were
constructed
via
the
imidization
reaction
between
phthalocyanine-based
tetraanhydride
and
1,3,5,7-tetra(4-aminophenyl)adamantine.
These
two
are
made
up
interpenetrated
pts
networks
according
to
powder
X-ray
diffraction
gas
adsorption
analyses.
CoPc-PI-COF-3
doped
carbon
black
has
been
employed
fabricate
electrocatalytic
cathode
towards
CO2
reduction
within
KHCO3
aqueous
solution,
displaying
Faradaic
efficiency
88-96
%
for
-to-CO
conversion
at
voltage
range
ca.
-0.60
-1.00
V
(vs.
RHE).
In
particular,
porous
structure
enables
active
centers
occupying
32.7
total
cobalt-phthalocyanine
subunits,
thus
giving
a
large
current
density
(jCO
)
-31.7
mA
cm-2
-0.90
V.
parameters
significantly
improved
than
excellent
2D
COF
analogue
(CoPc-PI-COF-1,
5.1
-21.2
).
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(23), С. 12742 - 12746
Опубликована: Март 20, 2021
Abstract
Achieving
a
selective
2
e
−
or
4
oxygen
reduction
reaction
(ORR)
is
critical
but
challenging.
Herein,
we
report
controlling
ORR
selectivity
of
Co
porphyrins
by
tuning
only
steric
effects.
We
designed
porphyrin
1
with
meso
‐phenyls
each
bearing
bulky
ortho
‐amido
group.
Due
to
the
resulted
hinderance,
has
four
atropisomers
similar
electronic
structures
dissimilar
Isomers
αβαβ
and
αααα
catalyze
n
=2.10
3.75
(
electron
number
transferred
per
O
),
respectively,
ααββ
αααβ
show
poor
=2.89–3.10.
Isomer
catalyzes
preventing
bimolecular
activation
path,
while
improves
improving
binding
at
its
pocket,
feature
confirmed
spectroscopy
methods,
including
K‐edge
near‐edge
X‐ray
absorption
fine
structure.
This
work
represents
an
unparalleled
example
improve
effects
without
changing
molecular
structures.