Nano Letters,
Год журнала:
2024,
Номер
24(45), С. 14363 - 14372
Опубликована: Ноя. 1, 2024
Deeply
understanding
how
local
microstrain
environment
around
diatomic
sites
influences
their
electronic
state
and
adsorption
is
crucial
for
improving
electrochemical
CO2
reduction
(eCO2R)
reaction;
however,
precise
engineering
of
the
atomic
challenging.
Herein,
we
fabricate
Ag-CdTMT
electrocatalysts
with
AgN2S2–CdN2S2
by
anchoring
Ag
to
nodes
CdTMT
(TMT
=
2,4,6-trimercaptotriazine
anion)
coordination
polymers.
The
catalysts
achieve
approximately
100%
Faradaic
efficiency
CO
an
industrial
level
current
density
(∼200
mA
cm–2
in
H-cell).
embedded
atoms
induce
formation
Ag–Cd
microstrain,
stretching
Cd–N/S
bonds,
reinforcing
electron
localization
at
Cd
sites.
adjacent
synergistically
reduced
4d–C
2p
antibonding
orbital
occupancy
intensifying
*COOH
as
rate-determining
step.
This
study
provides
novel
insights
into
customizing
structure
through
strain
engineering.
ABSTRACT
Copper
(Cu)
is
the
most
promising
catalyst
for
electrochemical
CO
2
‐to‐C
2+
conversion,
whereas
performance
remains
below
practical
thresholds
due
to
high
energy
barrier
of
C−C
coupling
and
lack
effective
approaches
steer
reaction
pathway.
Recent
advances
show
that
metal‐organic
frameworks
(MOF)
could
be
a
platform
as
support,
pre‐catalyst,
co‐catalyst
modify
electronic
structure
local
environment
Cu
catalysts
promoting
reduction
by
virtue
their
great
tunability
over
compositions
pore
architectures.
In
this
review,
we
discussed
general
design
principles,
catalytic
mechanisms,
achievements
MOF‐based
catalysts,
aiming
boost
refinement
steering
pathway
C
products.
The
fundamentals
challenges
are
first
introduced.
Then,
summarized
conceptions
from
three
aspects:
engineering
properties
Cu,
regulating
environment,
managing
site
exposure
mass
transport.
Further,
latest
progress
products
namely
Cu‐based
MOF,
MOF‐derived
Cu@MOF
hybrid
discussed.
Finally,
future
research
opportunities
strategies
suggested
innovate
rational
advanced
electrifying
transformation.
Analytical Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 13, 2025
The
elementary
mechanism
and
site
studies
of
nanozyme-based
inhibition
reactions
are
ambiguous
urgently
require
advanced
nanozymes
as
mediators
to
elucidate
the
effect.
To
this
end,
we
develop
a
class
featuring
single
Cu–N
catalytic
configurations
B–O
sites
binding
on
porous
nitrogen-doped
carbon
substrate
(B6/CuSA)
for
inducing
modulable
transfer
at
atomic
level.
full
redistribution
electrons
across
sites,
induced
by
incorporation,
yields
B6/CuSA
with
enhanced
peroxidase-like
activity
versus
CuSA.
More
importantly,
CuSA
features
in
cysteine
expresses
competitive
through
coordination
bonds,
an
constant
0.048
mM.
Benefiting
from
way
nanozymes,
possesses
mixed
approaches
noncovalent
bonds
delivers
record-mixed
interaction
0.054
mM
noncompetitive
0.71
Based
CuSA,
multichannel
sensor
array
accomplishes
detection
various
cancer
cells,
normal
thiols.
design
principle
work
is
endowed
guidelines
preliminary
evaluation
massive
potential
thiols,
cell
discrimination,
disease
prediction.
Advanced Energy Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 18, 2025
Abstract
Single
site
catalysts
(SSCs),
characterized
by
high
atomic
utilization
and
well‐defined
active
sites,
exhibit
significant
potential
in
the
field
of
CO
2
electroreduction
(CO
RR).
Typically,
SSCs
tend
to
a
2‐electron
transfer
reaction
RR,
there
remain
challenges
achieving
efficient
conversion
above
2‐electrons
(methane
(CH
4
)
multicarbon
products(C
2+
).
Therefore,
systematic
review
is
crucial
summarize
recent
advancements
single
electrocatalysts
their
structure‐activity
relationship.
The
discussion
begins
with
state‐of‐the‐art
characterization
techniques
SSCs.
Then
influence
central
atoms,
coordination
environments,
support
metal‐support
interactions
on
catalytic
performance
discussed
detail.
Subsequently,
regulation
strategies
improve
activity
selectivity
CH
C
products
are
discussed.
Furthermore,
dynamic
evolution
metal
sites
true
nature
during
RR
also
addressed.
Finally,
associated
for
product
formation
analyzed.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 17, 2024
The
electrocatalytic
reaction
pathway
is
highly
dependent
on
the
intrinsic
structure
of
catalyst.
CO2/CO
electroreduction
has
recently
emerged
as
a
potential
approach
for
obtaining
C2+
products,
but
it
challenging
to
achieve
high
selectivity
single
product.
Herein,
we
develop
Cu
atomic
ensemble
that
satisfies
appropriate
site
distance
and
coordination
environment
required
CO-to-acetate
conversion,
which
shows
outstanding
overall
performance
with
an
acetate
Faradaic
efficiency
70.2%
partial
current
density
225
mA
cm–2
formation
rate
2.1
mmol
h–1
cm–2.
Moreover,
single-pass
CO
conversion
91%
remarkable
stability
can
be
also
obtained.
Detailed
experimental
theoretical
investigations
confirm
significant
advantages
ensembles
in
optimizing
C–C
coupling,
stabilizing
key
ketene
intermediate
(*CCO),
inhibiting
*HOCCOH
intermediate,
switch
reduction
from
ethanol/ethylene
conventional
metallic
ensembles.
ACS Applied Nano Materials,
Год журнала:
2024,
Номер
7(15), С. 18027 - 18035
Опубликована: Июль 30, 2024
Developing
efficient
MnO2-based
bifunctional
catalysts
is
a
considerable
challenge
due
to
slow
oxygen
reduction
reaction
(ORR)
kinetics
and
the
limited
activity
of
evolution
(OER).
Herein,
an
catalyst
Ni/α-MnO2
prepared
by
straightforward
solid-phase
synthesis
method,
enabling
anchoring
Ni
atoms
onto
α-MnO2
surface.
The
electrochemically
active
surface
area
significantly
enhanced
generation
vacancies
presence
atomic
sites.
After
decoration,
half-wave
potential
ORR
elevated
0.82
V,
while
overpotential
for
OER
reduced
366
mV,
resulting
in
exceptionally
low
overall
(ΔE
=
0.79
V).
Density
functional
theory
calculations
reveal
that
d-band
center
Mn
exhibits
negative
shifts,
consequently
lowering
energy
barrier
conversion
OOH*
O*
OH*
OER.
In
secondary
zinc–air
battery,
supreme
power
density
290
mW
cm–2
acquired
at
current
350
mA
cm–2,
surpassing
performance
pristine
α-MnO2.
This
work
offers
valuable
guidance
development
high-performance
catalysts.
Journal of Materials Chemistry A,
Год журнала:
2024,
Номер
12(32), С. 20578 - 20605
Опубликована: Янв. 1, 2024
Molecular
engineering
of
MOF-based
electrocatalysts
for
the
CO
2
RR,
computational
simulations,
and
advanced
characterization
studies
are
discussed
summarized
to
illustrate
correlation
between
their
structure
performance.
It
is
of
great
significance
for
the
development
hydrogen
energy
technology
by
exploring
new-type
and
high-efficiency
electrocatalysts
(such
as
single
atom
catalysts
(SACs))
water
splitting.
In
this
paper,
combining
interface
engineering
doping
engineering,
a
unique
iron
(Fe)-doped
carbon-coated
nickel
sulfide
(Ni
Advanced Functional Materials,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 15, 2025
Abstract
Atomic‐level
metal
sites
at
the
edges
of
graphene‐like
carbon
supports
are
considered
more
active
for
CO
2
electrocatalysis
than
those
in‐plane.
However,
creating
high‐density
edge‐dominating
sites,
particularly
in
a
simple,
scalable,
and
self‐templated
fashion,
presents
significant
challenge.
Herein,
MOF‐mediated
self‐exfoliation
strategy
is
reported
to
preferentially
integrate
edge‐type
FeN
4
onto
ultrathin
edge‐rich
N‐doped
graphene
nanomesh
(e‐Fe‐NGM).
Theoretical
calculations,
finite
element
method
(FEM)
simulations,
together
with
series
situ
spectro‐electrochemical
experiments
corroborate
that
can
not
only
optimize
electronic
structure
catalysts,
facilitating
formation
*
COOH
desorption
CO,
but
also
effectively
induce
strong
local
electrostatic
field,
promoting
interfacial
H
O
supply
thereby
accelerating
protonation
process
.
Thus‐prepared
e‐Fe‐NGM
delivers
remarkable
Faraday
efficiency
(FE)
above
98%
over
an
ultra‐wide
potential
window
500
mV
high
turnover
frequency
6648
h
−1
,
much
superior
controlled
sample
dominant
plane‐type
sites.
Moreover,
this
self‐exfoliated,
non‐catalyzed
approach
readily
scalable
be
used
produce
large‐size
industrial
levels.
