Abstract
Dual‐Active‐Sites
Single‐Atom
catalysts
(DASs
SACs)
are
not
only
the
improvement
of
SACs
but
also
expansion
dual‐atom
catalysts.
The
DASs
contains
dual
active
sites,
one
which
is
a
single
atomic
site,
and
other
site
can
be
atom
or
type
endowing
with
excellent
catalytic
performance
wide
range
applications.
categorized
into
seven
types,
including
neighboring
mono
metallic
SACs,
bonded
non‐bonded
bridged
asymmetric
metal
nonmetal
combined
space
separated
SACs.
Based
on
above
classification,
general
methods
for
preparation
comprehensively
described,
especially
their
structural
characteristics
discussed
in
detail.
Meanwhile,
in‐depth
assessments
variety
applications
electrocatalysis,
thermocatalysis
photocatalysis
provided,
as
well
unique
mechanism
addressed.
Moreover,
prospects
challenges
related
highlighted.
authors
believe
great
expectations
this
review
will
provide
novel
conceptual
methodological
perspectives
exciting
opportunities
further
development
application
Advanced Energy Materials,
Год журнала:
2022,
Номер
13(2)
Опубликована: Ноя. 23, 2022
Abstract
Suffering
from
the
competition
adsorption
between
oxygen
reduction
reaction
(ORR)
and
evolution
(OER),
development
of
high‐efficiency
electrocatalysts
with
bifunctional
properties
still
remains
a
challenge.
Herein,
novel
effective
neodymium‐evoked
valence
electronic
perturbation
strategy
to
improve
balance
reversible
electrocatalysis
metallic
cobalt
sites
is
proposed.
To
heighten
coupling
Nd
Co,
metal‐organic‐framework‐induced
method
chosen
prepare
target
catalyst
atomic
Nd‐doped
Co
on
an
N‐doped
carbon
substrate.
The
as‐prepared
presents
excellent
electrocatalytic
low
overpotential
288
mV
at
10
mA
cm
−2
for
OER
high
half‐wave
potential
0.85
V
ORR.
robust
stabilities
both
ORR
are
also
proven.
electrochemical
in
situ
Raman
spectra
confirm
surface
dynamic
change
transformation
intermediates
by
noting
formation
Co–OOH.
Theoretical
calculations
verify
that
balanced
owing
strong
3d‐Nd
4f
orbital
effect
below
Fermi
level.
Moreover,
practicability
further
demonstrated
solid‐state
rechargeable
Zn‐Air
batteries,
which
exhibit
large
power
density
long
cycling
life.
Advanced Materials,
Год журнала:
2023,
Номер
35(32)
Опубликована: Май 3, 2023
Iron-nitrogen-carbon
(FeNC)
materials
have
emerged
as
a
promising
alternative
to
platinum-group
metals
for
catalyzing
the
oxygen
reduction
reaction
(ORR)
in
proton-exchange-membrane
fuel
cells.
However,
their
low
intrinsic
activity
and
stability
are
major
impediments.
Herein,
an
FeN-C
electrocatalyst
with
dense
FeN4
sites
on
hierarchically
porous
carbons
highly
curved
surfaces
(denoted
-hcC)
is
reported.
The
-hcC
catalyst
displays
exceptional
ORR
acidic
media,
high
half-wave
potential
of
0.85
V
(versus
reversible
hydrogen
electrode)
0.5
m
H2
SO4
.
When
integrated
into
membrane
electrode
assembly,
corresponding
cathode
maximum
peak
power
density
0.592
W
cm-2
demonstrates
operating
durability
over
30
000
cycles
under
harsh
/air
conditions,
outperforming
previously
reported
Fe-NC
electrocatalysts.
These
experimental
theoretical
studies
suggest
that
carbon
support
fine-tunes
local
coordination
environment,
lowers
energies
Fe
d-band
centers,
inhibits
adsorption
oxygenated
species,
which
can
enhance
stability.
This
work
provides
new
insight
nanostructure-activity
correlation
catalysis.
It
also
offers
approach
designing
advanced
single-metal-site
catalysts
energy-conversion
applications.
Abstract
In
recent
years,
some
experiments
and
theoretical
work
have
pointed
out
that
diatomic
catalysts
not
only
retain
the
advantages
of
monoatomic
catalysts,
but
also
introduce
a
variety
interactions,
which
exceed
limit
catalytic
performance
can
be
applied
to
many
fields.
Here,
interaction
between
adjacent
metal
atoms
in
is
elaborated:
synergistic
effect,
spacing
enhancement
effect
(geometric
effect),
electronic
effect.
With
regard
classification
characterization
various
new
are
classified
into
four
categories:
heteronuclear/homonuclear,
with/without
carbon
carriers,
their
measures
introduced
explained
detail.
aspect
preparation
widely
used
atomic
layer
deposition
method,
metal–organic
framework
derivative
simple
ball
milling
method
introduced,
with
emphasis
on
formation
mechanism
catalysts.
Finally,
effective
control
strategies
key
applications
electrocatalysis,
photocatalysis,
thermal
catalysis,
other
fields
given.
The
development
of
highly
active
carbon-based
bifunctional
electrocatalysts
for
both
the
oxygen
evolution
reaction
(OER)
and
reduction
(ORR)
is
desired,
but
still
full
challenges
in
rechargeable
Zn-air
batteries.
Metal
organic
frameworks
(MOFs)
covalent
(COFs)
have
gained
great
attention
various
applications
due
to
their
attractive
features
structural
tunability,
high
surface
area
porosity.
Herein,
a
core-shell
structured
hybrid
electrocatalyst
(H-NSC@Co/NSC),
which
contains
density
sites
MOF-derived
shell
(Co/NSC)
COF-derived
hollow
core
(H-NSC),
successfully
fabricated
by
direct
pyrolysis
covalently-connected
COF@ZIF-67
hybrid.
H-NSC@Co/NSC
manifests
excellent
catalytic
properties
toward
OER
ORR
with
small
potential
gap
(∆E
=
0.75
V).
assembled
battery
exhibits
power-density
204.3
mW
cm-2
stable
rechargeability,
outperforming
that
Pt/C+RuO2
battery.
Density
functional
theory
calculations
reveal
electronic
structure
carbon
on
Co/NSC
can
be
effectively
modulated
embedded
Co
nanoparticles
(NPs),
facilitating
adsorption
intermediates
leading
enhanced
activity.
This
work
will
provide
strategy
design
highly-efficient
application
energy
conversion
storage.
ACS Nano,
Год журнала:
2023,
Номер
17(10), С. 8918 - 8934
Опубликована: Май 2, 2023
Hollow
covalent
organic
frameworks
(COFs)
have
gained
significant
attention
because
of
their
specific
properties,
including
enhanced
surface-to-volume
ratio,
large
surface
area,
hierarchical
structure,
highly
ordered
nanostructures,
and
excellent
chemical
stability.
These
intrinsic
characteristics
endow
hollow
COFs
with
fascinating
physicochemical
properties
make
them
attractive
for
widespread
applications,
such
as
catalysis,
energy
storage,
drug
delivery,
therapy,
sensing,
environmental
remediation.
This
review
focuses
on
the
recent
developments
in
synthesis
derivatives.
In
addition,
practical
applications
various
fields
are
summarized.
Finally,
challenges
future
opportunities
terms
synthetic
methodologies
discussed.
expected
to
play
an
important
role
materials
science.
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Окт. 20, 2023
Highly
effective
and
selective
noble
metal-free
catalysts
attract
significant
attention.
Here,
a
single-atom
iron
catalyst
is
fabricated
by
saturated
adsorption
of
trace
onto
zeolitic
imidazolate
framework-8
(ZIF-8)
followed
pyrolysis.
Its
performance
toward
catalytic
transfer
hydrogenation
furfural
comparable
to
state-of-the-art
up
four
orders
higher
than
other
Fe
catalysts.
Isotopic
labeling
experiments
demonstrate
an
intermolecular
hydride
mechanism.
First
principles
simulations,
spectroscopic
calculations
experiments,
kinetic
correlations
reveal
that
the
synthesis
creates
pyrrolic
Fe(II)-plN3
as
active
center
whose
flexibility
manifested
being
pulled
out
plane,
enabled
defects,
crucial
for
collocating
reagents
allowing
chemistry
proceed.
The
catalyzes
chemoselectively
several
substrates
possesses
unique
trait
whereby
hindered
more
acidic
hydrogen
donors.
This
work
paves
way
noble-metal
free
important
chemical
reactions.
Advanced Functional Materials,
Год журнала:
2023,
Номер
34(11)
Опубликована: Ноя. 27, 2023
Abstract
Covalent
organic
frameworks
(COFs)
are
crystalline
porous
polymers
that
can
be
precisely
integrated
by
building
blocks
to
achieve
pre‐designed
composition,
components,
and
functions,
making
them
a
powerful
platform
for
the
development
of
molecular
devices
in
field
electrocatalysis.
The
precise
control
channel/dopant
positions
highly
ordered
network
structures
COFs
provide
an
ideal
material
system
applications
advanced
In
this
paper,
topological
structure
design
synthesis
methods
reviewed
detail,
their
principles
deeply
analyzed.
addition,
derivatives
electrocatalysis
systematically
summarized
optimization
strategies
proposed.
Finally,
application
prospects
challenges
may
encountered
future
prospected,
providing
helpful
guidance
research.
Advanced Materials,
Год журнала:
2023,
Номер
35(11)
Опубликована: Янв. 3, 2023
Supported
metal
catalysts
have
played
an
important
role
in
optimizing
selective
semihydrogenation
of
alkynes
for
fine
chemicals.
There
into,
nitrogen-doped
carbons,
as
a
type
promising
support
materials,
attracted
extensive
attentions.
However,
due
to
the
general
phenomenon
random
doping
nitrogen
species
support,
it
is
still
atremendous
challenge
finely
identify
which
configuration
dominates
catalytic
property
alkynes'
semihydrogenation.
Herein,
reported
that
uniform
mesoporous
N-doped
carbon
spheres
derived
from
polypyrrole
are
used
supports
immobilized
subnanometric
Pd
clusters,
provide
particular
platform
research
influence
configurations
on
Comprehensive
experimental
results
and
density
functional
theory
calculation
indicate
pyridinic
behavior
clusters.
The
high
contents
sites
offer
abundant
coordination
sites,
greatly
reduces
energy
barrier
rate-determining
reaction
step
makes
clusters
own
activity.
electron
effect
between
highly
selective.
Additionally,
good
mesostructures
also
promote
fast
transport
substrate.
Based
above,
catalyst
Pd@PPy-600
exhibits
activity
(99%)
selectivity
(96%)
phenylacetylene
(C8
H6
)
