ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 6141 - 6149
Опубликована: Апрель 1, 2025
Electrochemical
nitrate
reduction
(NO3RR)
is
primarily
hampered
by
high
energy
barriers
associated
with
the
rate-determining
step
(RDS),
which
involves
conversion
of
*NO3
to
*NO2,
and
selectivity-determining
(SDS)
from
*NO
*NHO.
Herein,
we
exhibit
a
molecular
catalyst,
Cu(I)-phen-SCN,
where
S
SCN
ligand
has
highest
polarizability
lowest
electronegativity
compared
C
or
N.
The
optimized
electronic
structure
catalyst
effectively
reduces
barrier
RDS
SDS
simultaneously.
In
situ
impedance
infrared
spectroscopy
revealed
that
Cu(I)-phen-SCN
exhibits
fastest
early
reaction
kinetics,
deeply
reducing
generate
intermediates
at
an
extremely
low
potential
(+0.2
V
vs
RHE).
As
result,
resulting
can
achieve
ammonia
synthesis
Faradaic
efficiency
N-selectivity
close
∼100%
yields
as
241.20
±
10.82
mg
h–1
mgcat–1.
X-ray
absorption
(XAS)
attenuated
total
reflection-Fourier
transform
(ATR-FTIR)
measurements
have
shown
maintained
in
dynamically
stable
state
throughout
electrochemical
processes,
exhibiting
excellent
catalytic
durability.
This
work
proposes
new
method
lower
nitrate-based
reactions,
providing
effective
strategy
improve
synthesis.
Chemical Society Reviews,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 11, 2024
The
core
of
clean
energy
technologies
such
as
fuel
cells,
water
electrolyzers,
and
metal-air
batteries
depends
on
a
series
oxygen
hydrogen-based
electrocatalysis
reactions,
including
the
reduction
reaction
(ORR),
evolution
(OER)
hydrogen
(HER),
which
necessitate
cost-effective
electrocatalysts
to
improve
their
efficiency.
In
recent
decade,
complex
metal
oxides
(beyond
simple
transition
oxides,
spinel
ABO
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Окт. 25, 2024
Supramolecular
polymers
possess
great
potential
in
catalysis
owing
to
their
distinctive
molecular
recognition
and
dynamic
crosslinking
features.
However,
investigating
supramolecular
electrocatalysts
with
high
efficiency
oxygen
reduction
reaction
hydrogen
peroxide
(ORHP)
remains
an
unexplored
frontier.
Herein,
we
present
organic
for
ORHP
by
introducing
cyclodextrin-containing
noncovalent
building
blocks,
affording
these
supramolecules
abundant
bonds.
The
electronic
states
kinetics
are
further
well-modulated
via
a
host-guest
strategy,
resulting
appropriate
regional
electron
binding
force
controllable
chemical
activity.
Notably,
integrating
units
into
phenyl
group-containing
model
covalent
polymer
achieves
production
rate
of
9.14
mol
g
ABSTRACT
Carbon
electrocatalyst
materials
based
on
lignocellulosic
biomass
with
multi‐components,
various
dimensions,
high
carbon
content,
and
hierarchical
morphology
structures
have
gained
great
popularity
in
electrocatalytic
applications
recently.
Due
to
the
catalytic
deficiency
of
neutral
atoms,
usage
single
lignocellulosic‐based
electrocatalysis
involving
energy
storage
conversion
presents
unsatisfactory
applicability.
However,
atomic‐level
modulation
lignocellulose‐based
can
optimize
electronic
structures,
charge
separation,
transfer
processes,
so
forth,
which
results
substantially
enhanced
performance
carbon‐based
catalysts.
This
paper
reviews
recent
advances
rational
design
as
electrocatalysts
from
an
perspective,
such
self/external
heteroatom
doping
metal
modification.
Then,
through
systematic
discussion
principles
reaction
mechanisms
catalysts,
prepared
catalysts
rechargeable
batteries
are
reviewed.
Finally,
challenges
improving
prospects
diverse
review
contributes
synthesis
strategy
via
modulation,
turn
promotes
lignocellulose
valorization
for
conversion.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(26)
Опубликована: Апрель 19, 2024
Abstract
Conjugated
polymers
with
tailorable
composition
and
microarchitecture
are
propitious
for
modulating
catalytic
properties
deciphering
inherent
structure‐performance
relationships.
Herein,
we
report
a
facile
linker
engineering
strategy
to
manipulate
the
electronic
states
of
metallophthalocyanine
conjugated
uncover
vital
role
organic
linkers
in
facilitating
electrocatalytic
oxygen
reduction
reaction
(ORR).
Specifically,
set
cobalt
phthalocyanine
(CoPc‐CPs)
wrapped
onto
carbon
nanotubes
(denoted
CNTs@CoPc‐CPs)
judiciously
crafted
via
situ
assembling
square‐planar
tetraaminophthalocyanine
(CoPc(NH
2
)
4
different
linear
aromatic
dialdehyde‐based
presence
CNTs.
Intriguingly,
upon
varying
characteristic
from
terephthalaldehyde
(TA)
2,5‐thiophenedicarboxaldehyde
(TDA)
then
thieno/thiophene‐2,5‐dicarboxaldehyde
(bTDA),
their
corresponding
CNTs@CoPc‐CPs
exhibit
gradually
improved
ORR
performance.
More
importantly,
theoretical
calculations
reveal
that
charge
transfer
CoPc
units
electron‐withdrawing
(i.e.,
TDA
bTDA)
drives
delocalization
Co
d‐orbital
electrons,
thereby
downshifting
d‐band
energy
level.
Accordingly,
active
centers
more
positive
valence
state
optimized
binding
toward
ORR‐relevant
intermediates
thus
balanced
adsorption/desorption
pathway
endows
significant
enhancement
ORR.
This
work
demonstrates
molecular‐level
route
rationally
designing
efficient
polymer
catalysts
gaining
insightful
understanding
mechanisms.
Materials,
Год журнала:
2024,
Номер
17(15), С. 3698 - 3698
Опубликована: Июль 26, 2024
This
review
comprehensively
addresses
the
developments
and
applications
of
polymer
materials
in
optoelectronics.
Especially,
this
introduces
how
absorb,
emit,
transfer
charges,
including
exciton–vibrational
coupling,
nonradiative
radiative
processes,
Förster
Resonance
Energy
Transfer
(FRET),
energy
dynamics.
Furthermore,
it
outlines
charge
trapping
recombination
draws
corresponding
practical
implications.
The
following
section
focuses
on
application
organic
optoelectronics
devices
highlights
detailed
structure,
operational
principle,
performance
metrics
photovoltaic
cells
(OPVs),
light-emitting
diodes
(OLEDs),
photodetectors,
transistors
detail.
Finally,
study
underscores
transformative
impact
evolution
optoelectronics,
providing
a
comprehensive
understanding
their
properties,
mechanisms,
diverse
that
contribute
to
advancing
innovative
technologies
field.
