Advanced Materials,
Год журнала:
2021,
Номер
34(6)
Опубликована: Дек. 9, 2021
Single-atom
catalysts
(SACs)
are
witnessing
rapid
development
due
to
their
high
activity
and
selectivity
toward
diverse
reactions.
However,
it
remains
a
grand
challenge
in
the
general
synthesis
of
SACs,
particularly
featuring
an
identical
chemical
microenvironment
on
same
support.
Herein,
universal
synthetic
protocol
is
developed
immobilize
SACs
metal-organic
frameworks
(MOFs).
Significantly,
by
means
SnO2
as
mediator
or
adaptor,
not
only
different
single-atom
metal
sites,
such
Pt,
Cu,
Ni,
etc.,
can
be
installed,
but
also
MOF
supports
changed
(for
example,
UiO-66-NH2
,
PCN-222,
DUT-67)
afford
M1
/SnO2
/MOF
architecture.
Taking
representative,
Pt1
exhibits
approximately
five
times
higher
photocatalytic
H2
production
than
corresponding
Pt
nanoparticles
(≈2.5
nm)
stabilized
/UiO-66-NH2
.
Remarkably,
despite
parameters
support
catalyst
possesses
hydrogen
evolution
rate
2167
µmol
g-1
h-1
superior
Cu1
Ni1
counterparts,
which
attributed
differentiated
binding
free
energies,
supported
density-functional
theory
(DFT)
calculations.
This
thought
first
report
approach
stabilization
with
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(12)
Опубликована: Янв. 7, 2022
Herein,
a
novel
dual
single-atom
catalyst
comprising
adjacent
Fe-N4
and
Mn-N4
sites
on
2D
ultrathin
N-doped
carbon
nanosheets
with
porous
structure
(FeMn-DSAC)
was
constructed
as
the
cathode
for
flexible
low-temperature
Zn-air
battery
(ZAB).
FeMn-DSAC
exhibits
remarkable
bifunctional
activities
oxygen
reduction
reaction
(ORR)
evolution
(OER).
Control
experiments
density
functional
theory
calculations
reveal
that
catalytic
activity
arises
from
cooperative
effect
of
Fe/Mn
dual-sites
aiding
*OOH
dissociation
well
nanosheet
promoting
active
sits
exposure
mass
transfer
during
process.
The
excellent
enables
ZAB
to
operate
efficiently
at
ultra-low
temperature
-40
°C,
delivering
30
mW
cm-2
peak
power
retaining
up
86
%
specific
capacity
room
counterpart.
Chemical Reviews,
Год журнала:
2023,
Номер
123(9), С. 6257 - 6358
Опубликована: Март 21, 2023
The
oxygen
evolution
reaction
(OER)
and
reduction
(ORR)
are
core
steps
of
various
energy
conversion
storage
systems.
However,
their
sluggish
kinetics,
i.e.,
the
demanding
multielectron
transfer
processes,
still
render
OER/ORR
catalysts
less
efficient
for
practical
applications.
Moreover,
complexity
catalyst–electrolyte
interface
makes
a
comprehensive
understanding
intrinsic
mechanisms
challenging.
Fortunately,
recent
advances
in
situ/operando
characterization
techniques
have
facilitated
kinetic
monitoring
under
conditions.
Here
we
provide
selected
highlights
mechanistic
studies
with
main
emphasis
placed
on
heterogeneous
systems
(primarily
discussing
first-row
transition
metals
which
operate
basic
conditions),
followed
by
brief
outlook
molecular
catalysts.
Key
sections
this
review
focused
determination
true
active
species,
identification
sites,
reactive
intermediates.
For
in-depth
insights
into
above
factors,
short
overview
metrics
accurate
characterizations
is
provided.
A
combination
obtained
time-resolved
information
reliable
activity
data
will
then
guide
rational
design
new
Strategies
such
as
optimizing
restructuring
process
well
overcoming
adsorption-energy
scaling
relations
be
discussed.
Finally,
pending
current
challenges
prospects
toward
development
homogeneous
presented.
Advanced Materials,
Год журнала:
2023,
Номер
35(14)
Опубликована: Янв. 11, 2023
Single-atom
catalysts
(SACs)
have
attracted
extensive
interest
to
catalyze
the
oxygen
reduction
reaction
(ORR)
in
fuel
cells
and
metal-air
batteries.
However,
development
of
SACs
with
high
selectivity
long-term
stability
is
a
great
challenge.
In
this
work,
carbon
vacancy
modified
Fe-N-C
(FeH
-N-C)
are
practically
designed
synthesized
through
microenvironment
modulation,
achieving
high-efficient
utilization
active
sites
optimization
electronic
structures.
The
FeH
-N-C
catalyst
exhibits
half-wave
potential
(E1/2
)
0.91
V
sufficient
durability
100
000
voltage
cycles
29
mV
E1/2
loss.
Density
functional
theory
(DFT)
calculations
confirm
that
vacancies
around
metal-N4
can
reduce
adsorption
free
energy
OH*,
hinder
dissolution
metal
center,
significantly
enhancing
ORR
kinetics
stability.
Accordingly,
presented
high-power
density
over
1200
h
rechargeable
zinc-air
batteries
(ZABs).
This
work
will
not
only
guide
for
developing
highly
stable
rational
modulation
sites,
but
also
provide
an
insight
into
structure
boost
electrocatalytical
performances.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(6), С. 3647 - 3655
Опубликована: Фев. 6, 2023
Nitrogen-doped
graphitic
carbon
materials
hosting
single-atom
iron
(Fe-N-C)
are
major
non-precious
metal
catalysts
for
the
oxygen
reduction
reaction
(ORR).
The
nitrogen-coordinated
Fe
sites
described
as
first
coordination
sphere.
As
opposed
to
good
performance
in
ORR,
that
evolution
(OER)
is
extremely
poor
due
sluggish
O-O
coupling
process,
thus
hampering
practical
applications
of
rechargeable
zinc
(Zn)-air
batteries.
Herein,
we
succeed
boosting
OER
activity
Fe-N-C
by
additionally
incorporating
phosphorus
atoms
into
second
sphere,
here
denoted
P/Fe-N-C.
resulting
material
exhibits
excellent
0.1
M
KOH
with
an
overpotential
low
304
mV
at
a
current
density
10
mA
cm-2.
Even
more
importantly,
they
exhibit
remarkably
small
ORR/OER
potential
gap
0.63
V.
Theoretical
calculations
using
first-principles
functional
theory
suggest
enhances
electrocatalytic
balancing
*OOH/*O
adsorption
FeN4
sites.
When
used
air
cathode
Zn-air
battery,
P/Fe-N-C
delivers
charge-discharge
high
peak
power
269
mW
cm-2,
highlighting
its
role
state-of-the-art
bifunctional
electrocatalyst.
Advanced Materials,
Год журнала:
2021,
Номер
33(49)
Опубликована: Сен. 24, 2021
Abstract
Hydrogen
peroxide
(H
2
O
)
is
an
environment‐friendly
and
efficient
oxidant
with
a
wide
range
of
applications
in
different
industries.
Recently,
the
production
hydrogen
through
direct
electrosynthesis
has
attracted
widespread
research
attention,
emerged
as
most
promising
method
to
replace
traditional
energy‐intensive
multi‐step
anthraquinone
process.
In
ongoing
efforts
achieve
highly
large‐scale
H
,
carbon‐based
materials
have
been
developed
2e
−
oxygen
reduction
reaction
catalysts,
benefits
low
cost,
abundant
availability,
optimal
performance.
This
review
comprehensively
introduces
strategies
for
optimizing
toward
production,
latest
advances
hybrid
catalysts.
The
active
sites
influence
coordination
heteroatom
doping
on
selectivity
are
extensively
analyzed.
particular,
appropriate
design
functional
groups
understanding
effect
electrolyte
pH
expected
further
improve
selective
efficiency
producing
via
reaction.
Methods
improving
catalytic
activity
by
interface
engineering
kinetics
summarized.
Finally,
challenges
catalysts
face
before
they
can
be
employed
commercial‐scale
identified,
prospects
designing
novel
electrochemical
reactors
proposed.
Advanced Materials,
Год журнала:
2022,
Номер
34(16)
Опубликована: Фев. 22, 2022
Electrocatalytic
hydrogen
peroxide
(H2
O2
)
synthesis
via
the
two-electron
oxygen
reduction
reaction
(2e
ORR)
pathway
is
becoming
increasingly
important
due
to
green
production
process.
Here,
cationic
vacancies
on
nickel
phosphide,
as
a
proof-of-concept
regulate
catalyst's
physicochemical
properties,
are
introduced
for
efficient
H2
electrosynthesis.
The
as-fabricated
Ni
(VNi
)-enriched
Ni2-x
P-VNi
electrocatalyst
exhibits
remarkable
2e
ORR
performance
with
molar
fraction
of
>95%
and
Faradaic
efficiencies
>90%
in
all
pH
conditions
under
wide
range
applied
potentials.
Impressively,
as-created
VNi
possesses
superb
long-term
durability
over
50
h,
suppassing
recently
reported
catalysts
Operando
X-ray
absorption
near-edge
spectroscopy
(XANES)
synchrotron
Fourier
transform
infrared
(SR-FTIR)
combining
theoretical
calculations
reveal
that
excellent
catalytic
originates
from
-induced
geometric
electronic
structural
optimization,
thus
promoting
adsorption
favored
"end-on"
configuration.
It
believed
demonstrated
cation
vacancy
engineering
an
effective
strategy
toward
creating
active
heterogeneous
atomic
precision.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(29)
Опубликована: Май 6, 2022
Abstract
Simultaneous
regulation
of
the
coordination
environment
single‐atom
catalysts
(SACs)
and
engineering
architectures
with
efficient
exposed
active
sites
are
strategies
for
boosting
peroxymonosulfate
(PMS)
activation.
We
isolated
cobalt
atoms
dual
nitrogen
oxygen
(Co−N
3
O
1
)
on
oxygen‐doped
tubular
carbon
nitride
(TCN)
by
pyrolyzing
a
hydrogen‐bonded
cyanuric
acid
melamine–cobalt
acetate
precursor.
The
theoretically
constructed
Co−N
moiety
TCN
exhibited
an
impressive
mass
activity
7.61×10
5
min
−1
mol
high
2
selectivity.
Theoretical
calculations
revealed
that
single
occupied
environment,
PMS
adsorption
was
promoted
energy
barriers
reduced
key
*O
intermediate
produced
.
were
attached
to
widely
used
poly(vinylidene
fluoride)
microfiltration
membrane
deliver
antibiotic
wastewater
treatment
system
97.5
%
ciprofloxacin
rejection
over
10
hours,
thereby
revealing
suitability
industrial
applications.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(32)
Опубликована: Май 31, 2022
Abstract
Manipulating
the
coordination
environment
of
active
center
via
anion
modulation
to
reveal
tailored
activity
and
selectivity
has
been
widely
achieved,
especially
for
carbon‐based
single‐atom
site
catalysts
(SACs).
However,
tuning
ligand
fields
by
single‐site
metal
cation
regulation
identifying
effects
on
resulting
electronic
configuration
is
seldom
explored.
Herein,
we
propose
a
Ru
strategy
engineer
properties
constructing
Ru/LiCoO
2
SAC
with
atomically
dispersed
Ru−Co
pair
sites.
Benefitting
from
strong
coupling
between
Co
sites,
catalyst
possesses
an
enhanced
electrical
conductivity
achieves
near‐optimal
oxygen
adsorption
energies.
Therefore,
optimized
delivers
superior
evolution
reaction
(OER)
low
overpotential,
high
mass
1000
A
g
oxide
−1
at
small
overpotential
335
mV,
excellent
long‐term
stability.
It
also
exhibits
rapid
kinetics
rate
capability
outstanding
durability
in
zinc–air
battery.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(12)
Опубликована: Янв. 19, 2022
The
in-depth
understanding
of
local
atomic
environment-property
relationships
p-block
metal
single-atom
catalysts
toward
the
2
e-
oxygen
reduction
reaction
(ORR)
has
rarely
been
reported.
Here,
guided
by
first-principles
calculations,
we
develop
a
heteroatom-modified
In-based
metal-organic
framework-assisted
approach
to
accurately
synthesize
an
optimal
catalyst,
in
which
single
In
atoms
are
anchored
combined
N,S-dual
first
coordination
and
B
second
supported
hollow
carbon
rods
(In
SAs/NSBC).
SAs/NSBC
catalyst
exhibits
high
H2
O2
selectivity
above
95
%
wide
range
pH.
Furthermore,
SAs/NSBC-modified
natural
air
diffusion
electrode
unprecedented
production
rate
6.49
mol
peroxide
gcatalyst-1
h-1
0.1
M
KOH
electrolyte
6.71
PBS
electrolyte.
This
strategy
enables
design
next-generation
high-performance
materials,
provides
practical
guidance
for
electrosynthesis.