Abstract
Electrocatalytic
hydrogen
evolution
reaction
(HER)
is
a
promising
strategy
to
solve
and
mitigate
the
coming
energy
shortage
global
environmental
pollution.
Searching
for
efficient
electrocatalysts
HER
remains
challenging
through
traditional
trial‐and‐error
methods
from
numerous
potential
material
candidates.
Theoretical
high
throughput
calculation
assisted
by
machine
learning
possible
method
screen
excellent
effectively.
This
will
pave
way
high‐efficiency
low‐price
electrocatalyst
findings.
In
this
review,
we
comprehensively
introduce
workflow
standard
models
reduction
reactions.
mainly
illustrates
how
used
in
catalyst
filtration
descriptor
exploration.
Subsequently,
several
applications,
including
surface
electrocatalysts,
two‐dimensional
(2D)
single/dual
atom
using
electrocatalytic
HER,
are
highlighted
introduced.
Finally,
corresponding
challenge
perspective
reactions
concluded.
We
hope
critical
review
can
provide
comprehensive
understanding
of
design
guide
future
theoretical
experimental
investigation
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(11)
Опубликована: Янв. 15, 2024
Abstract
Single
atom
catalysts
with
defined
local
structures
and
favorable
surface
microenvironments
are
significant
for
overcoming
slow
kinetics
accelerating
O
2
electroreduction.
Here,
enriched
tip‐like
FeN
4
sites
(T−Fe
SAC)
on
spherical
carbon
surfaces
were
developed
to
investigate
the
change
in
catalysis
behavior.
Finite
element
method
(FEM)
simulations,
together
experiments,
indicate
strong
electric
field
of
more
denser
interfacial
water
layer,
thereby
enhancing
proton‐coupled
electron
transfer
process.
In
situ
spectroelectrochemical
studies
density
functional
theory
(DFT)
calculation
results
pathway
transition
sites,
promoting
dissociation
O−O
bond
via
side‐on
adsorption
model.
The
adsorbed
OH*
can
be
facilely
released
curved
accelerate
oxygen
reduction
reaction
(ORR)
kinetics.
obtained
T−Fe
SAC
nanoreactor
exhibits
excellent
ORR
activities
(
E
1/2
=0.91
V
vs.
RHE)
remarkable
stability,
exceeding
those
flat
Pt/C.
This
work
clarified
in‐depth
insights
into
origin
catalytic
activity
held
great
promise
industrial
catalysis,
electrochemical
energy
storage,
many
other
fields.
Abstract
Ammonia,
a
vital
component
in
the
synthesis
of
fertilizers,
plastics,
and
explosives,
is
traditionally
produced
via
energy‐intensive
environmentally
detrimental
Haber–Bosch
process.
Given
its
considerable
energy
consumption
significant
greenhouse
gas
emissions,
there
growing
shift
toward
electrocatalytic
ammonia
as
an
eco‐friendly
alternative.
However,
developing
efficient
electrocatalysts
capable
achieving
high
selectivity,
Faraday
efficiency,
yield
under
ambient
conditions
remains
challenge.
This
review
delves
into
decades‐long
research
synthesis,
highlighting
evolution
fundamental
principles,
theoretical
descriptors,
reaction
mechanisms.
An
in‐depth
analysis
nitrogen
reduction
(NRR)
nitrate
(NitRR)
provided,
with
focus
on
their
electrocatalysts.
Additionally,
theories
behind
electrocatalyst
design
for
are
examined,
including
Gibbs
free
approach,
Sabatier
principle,
d
‐band
center
theory,
orbital
spin
states.
The
culminates
comprehensive
overview
current
challenges
prospective
future
directions
development
NRR
NitRR,
paving
way
more
sustainable
methods
production.
ACS Catalysis,
Год журнала:
2024,
Номер
14(9), С. 6816 - 6826
Опубликована: Апрель 18, 2024
The
Fe-embedded
N-doped
graphene
(Fe–N–C)
is
the
most
representative
single
atom
catalyst
(SAC)
that
has
shown
great
potentiality
in
electrocatalysis,
such
as
oxygen
reduction
reaction
(ORR)
and
evolution
(OER).
However,
active
moiety
of
Fe–N–C
still
elusive
due
to
contradictory
experimental
results.
Moreover,
early
simulations
mainly
focus
on
thermodynamic
potential
adsorbates,
while
effect
spin
multiplicity
receives
little
attention.
To
explore
role
we
employ
constant-potential
density
functional
theory
(DFT)
systematically
study
structural
high-spin
(HS)
intermediate-spin
(IS)
FeN4
site
(marked
by
FeN4HS/IS)
OER
ORR
processes.
With
consideration
multiplicity,
our
simulation
shows
spontaneous
oxidation
from
Fe(II)N4IS
Fe(III)N4HS
at
U
=
0.4
V
versus
SHE.
Further
indicates
FeN4IS
undergoes
a
sequential
adsorption
*OH
*OOH
along
with
increase,
which
leads
state
transition
IS
HS.
According
free
energy
analysis,
FeN4HS*OOH
confirmed
be
practical
centers
OER,
FeN4HS*OH
are
assigned
center
low
high
overpotentials.
predicted
activity
agrees
situ
X-ray
absorption
near-edge
spectroscopy
(XANES)
57Fe
Mössbauer
measurement
Xiao
et
al.
[Microporous
Framework
Induced
Synthesis
Single-Atom
Dispersed
Fe-NC
Acidic
Catalyst
its
In
Situ
Reduced
Fe-N4
Active
Site
Identification
Revealed
X-Ray
Absorption
Spectroscopy.
ACS
Catal.
2018,
8,
2824–2832].
Based
geometry
orbital
bond
length
Fe–N
coordination
number
Fe
found
have
significant
impact
d
splitting
thus
induce
turnover
HS/IS
stability
OER/ORR
intermediates.
Our
brings
comprehensive
insights
into
Fe–N–C,
reveals
significance
electrocatalysis
benefits
further
theoretical
design
SACs
perspective
effects.
Accounts of Chemical Research,
Год журнала:
2024,
Номер
57(2), С. 198 - 207
Опубликована: Янв. 3, 2024
ConspectusSingle
atom
electrocatalysts,
with
noble
metal-free
composition,
maximal
efficiency,
and
exceptional
reactivity
toward
various
energy
environmental
applications,
have
become
a
research
hot
spot
in
the
recent
decade.
Their
simplicity
isolated
nature
of
atomic
structure
their
active
site
also
made
them
an
ideal
model
catalyst
system
for
studying
reaction
mechanisms
activity
trends.
However,
state
single
sites
during
electrochemical
reactions
may
not
be
as
simple
is
usually
assumed.
To
contrary,
electrocatalysts
been
reported
to
under
greater
influence
from
interfacial
dynamics,
solvent
electrolyte
ions
perpetually
interacting
electrified
center
applied
electrode
potential.
These
complexities
render
trends
derived
simplistic
models
dubious.In
this
Account,
few
popular
electrocatalysis
systems,
we
show
how
change
potential
induces
nontrivial
variation
free
profile
elemental
steps,
demonstrate
centers
different
electronic
features
can
induce
solvation
structures
at
interface
even
same
intermediate
simplest
reaction,
discuss
implication
on
kinetics
thermodynamics
better
address
selectivity
We
venture
into
more
intriguing
phenomena,
such
alternative
pathways
intermediates
that
are
favored
stabilized
by
polarization
effects,
long-range
dynamics
across
region
far
beyond
contact
layer,
dynamic
activation
or
deactivation
operation
conditions.
necessity
including
realistic
aspects
(explicit
solvent,
electrolyte,
potential)
correctly
capture
physics
chemistry
understand
design
principles
fail
they
revised
factors
model.
All
these
rich
would
remain
hidden
overlooked
otherwise.
believe
complexity
curse
but
blessing
it
enables
deeper
understanding
finer
control
potential-dependent
landscape
reactions,
which
opens
up
new
dimensions
further
optimization
beyond.
Limitations
current
methods
challenges
faced
theoretical
experimental
communities
discussed,
along
possible
solutions
awaiting
development
future.
Advanced Functional Materials,
Год журнала:
2024,
Номер
34(34)
Опубликована: Апрель 25, 2024
Abstract
The
rapid
advancement
of
high‐performance
computing
and
artificial
intelligence
technology
has
opened
up
novel
avenues
for
the
development
various
metal
electrocatalysts.
In
particular,
dilute
high‐entropy
alloys
have
garnered
significant
attention
owing
to
their
unique
electronic
spatial
structures,
as
well
exceptional
electrocatalytic
performance.
Commencing
with
exploration
single‐atom
alloy
catalysts,
latest
advancements
in
machine
learning
(ML)
techniques
are
presented
efficient
screening
a
broad
spectrum
spaces.
Subsequently,
review
delves
into
prevailing
trend
research,
focusing
specifically
on
rare‐metal
electrocatalysts,
offers
an
overview
progress
outcomes
achieved
through
application
ML
these
domains.
Finally,
highlighted
promising
category
electrocatalysts
underscore
importance
potential
applications
addressing
complex
challenging
research
issues
underscored.
Accounts of Chemical Research,
Год журнала:
2024,
Номер
57(15), С. 2093 - 2104
Опубликована: Июнь 26, 2024
ConspectusLithium-sulfur
batteries
(LSBs),
recognized
for
their
high
energy
density
and
cost-effectiveness,
offer
significant
potential
advancement
in
storage.
However,
widespread
deployment
remains
hindered
by
challenges
such
as
sluggish
reaction
kinetics
the
shuttle
effect
of
lithium
polysulfides
(LiPSs).
By
introduction
catalytic
materials,
effective
adsorption
LiPSs,
smooth
surface
migration
behavior,
significantly
reduced
conversion
barriers
are
expected
to
be
achieved,
thereby
sharpening
electrochemical
fundamentally
addressing
aforementioned
challenges.
driven
practical
application
targets,
demand
higher
loadings
electrolyte
parameters
inevitably
exacerbates
burden
on
materials
during
service.
Additionally,
given
that
contribute
negligible
capacity,
incorporation
increases
mass
nonactive
components
reducing
LSBs.
A
meticulous
insight
into
lithium-sulfur
reveals
LiPSs
is
dominated
active
sites
surfaces
materials.
These
microregions
provide
necessary
electron
ion
transport
with
efficacy
quantity
directly
impacting
efficiency.
In
light
these
considerations,
strategic
optimization
emerges
a
paramount
pathway
toward
promoting
performance
LSBs
while
concurrently
mitigating
unnecessary
mass.
Here,
we
outline
three
strategies
developed
our
group
optimize
materials:
(1)
Augmenting
customizing
structural
modulation
precise
dimensional
control
maximize
exposure.
Emphasis
has
been
placed
approaches
material
synthesis
essence
reactions
achieving
this
strategy.
(2)
Regulating
microenvironment
integrating
coordination
refinement,
long-range
atomic
interactions,
metal-support
other
electronic
regulation
strategies,
providing
an
elevation
intrinsic
performance.
(3)
Implementing
self-cleaning
mechanism
counteract
deactivation
designing
tandem
adsorption-migration-transformation
sulfur
contained
within
molecular
domain.
Throughout
process,
mechanisms
driving
enhancement
through
site
have
prominently
emphasized,
which
encompass
aspects
structure,
composition,
configuration
expand
comprehension
Li-S
chemistry.
Subsequently,
considerations
demanding
heightened
attention
future
processes
delineated,
including
situ
evolution
patterns
resistance
poisoning
sites.
It
noteworthy
similarity
between
catalysis
chemistry
traditional
electrocatalytic
processes,
Account
elucidates
concept
drawing
insights
from
representative
works
own
field
electrocatalysis,
relatively
rare
previous
reviews
The
proposed
uncovering
introducing
innovative
ideas
optimization,
ultimately
advancing
stability
Abstract
The
oxygen
evolution
reaction
(OER)
performance
of
NiCo
LDH
electrocatalysts
can
be
improved
through
fluorine
doping.
roles
Ni
and
Co
active
sites
in
such
catalysts
remain
ambiguous
controversial.
In
addressing
the
issue,
this
study
draws
upon
molecular
orbital
theory
proposes
center
competitive
mechanism
between
Co.
doped
F‐atoms
directly
impact
valence
state
metal
atoms
or
exert
an
indirect
influence
dehydrogenation,
thereby
modulating
center.
As
are
progressively
aggregate,
e
g
orbitals
transition
from
2
to
1
,
subsequently
0
.
corresponding
elevates
+2
+3,
then
+4,
signifying
initial
increase
followed
by
a
subsequent
decrease
electrocatalytic
performance.
Furthermore,
series
F‐NiCo
synthesized
verify
occupancy
analysis,
catalytic
OER
overpotentials
303,
243,
240,
246
mV
at
current
density
10
mA
cm
−2
respectively,
which
coincides
well
with
theoretical
prediction.
This
investigation
not
only
provides
novel
mechanistic
insights
into
competition
but
also
establishes
foundation
for
design
high‐performance
catalysts.