Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(3), С. 2015 - 2023
Опубликована: Янв. 9, 2024
Understanding
the
size-dependent
behavior
of
nanoparticles
is
crucial
for
optimizing
catalytic
performance.
We
investigate
differences
in
selectivity
size-selected
gold
CO2
electroreduction
with
sizes
ranging
from
1.5
to
6.5
nm.
Our
findings
reveal
an
optimal
size
approximately
3
nm
that
maximizes
toward
CO,
exhibiting
up
60%
Faradaic
efficiency
at
low
potentials.
High-resolution
transmission
electron
microscopy
reveals
different
shapes
particles
and
suggests
multiply
twinned
are
favorable
reduction
CO.
analysis
shows
twin
boundaries
pin
8-fold
coordinated
surface
sites
turn
a
variation
shape
optimize
abundance
viable
path
electrocatalytic
This
work
contributes
advancement
nanocatalyst
design
achieving
tunable
conversion
into
valuable
products.
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Ноя. 22, 2023
The
underlying
mechanism
of
cation
effects
on
CO2RR
remains
debated.
Herein,
we
study
by
simulating
both
outer-sphere
electron
transfer
(OS-ET)
and
inner-sphere
(IS-ET)
pathways
during
via
constrained
density
functional
theory
molecular
dynamics
(cDFT-MD)
slow-growth
DFT-MD
(SG-DFT-MD),
respectively.
Our
results
show
without
any
cations,
only
OS-ET
is
feasible
with
a
barrier
1.21
eV.
In
the
presence
K+
(Li+),
shows
very
high
2.93
eV
(4.15
eV)
thus
being
prohibited.
However,
cations
promote
CO2
activation
through
IS-ET
0.61
(K+)
0.91
generating
key
intermediate
(adsorbed
CO[Formula:
see
text]).
Without
CO2-to-CO[Formula:
text](ads)
conversion
cannot
proceed.
findings
reveal
arise
from
short-range
Coulomb
interactions
reaction
intermediates.
These
disclose
that
modulate
inner-
CO2RR,
offering
substantial
insights
specificity
in
initial
steps.
Nano-Micro Letters,
Год журнала:
2023,
Номер
15(1)
Опубликована: Июль 11, 2023
Electrochemical
carbon
dioxide
reduction
reaction
(CO2RR)
provides
a
promising
way
to
convert
CO2
chemicals.
The
multicarbon
(C2+)
products,
especially
ethylene,
are
of
great
interest
due
their
versatile
industrial
applications.
However,
selectively
reducing
ethylene
is
still
challenging
as
the
additional
energy
required
for
C-C
coupling
step
results
in
large
overpotential
and
many
competing
products.
Nonetheless,
mechanistic
understanding
key
steps
preferred
pathways/conditions,
well
rational
design
novel
catalysts
production
have
been
regarded
approaches
achieving
highly
efficient
selective
CO2RR.
In
this
review,
we
first
illustrate
CO2RR
(e.g.,
adsorption/activation,
formation
*CO
intermediate,
step),
offering
conversion
ethylene.
Then
alternative
pathways
conditions
competitive
products
(C1
other
C2+
products)
investigated,
guiding
further
development
generation.
Engineering
strategies
Cu-based
CO2RR-ethylene
summarized,
correlations
mechanism/pathways,
engineering
selectivity
elaborated.
Finally,
major
challenges
perspectives
research
area
proposed
future
practical
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Май 5, 2023
Abstract
It
has
been
over
twenty
years
since
the
linear
scaling
of
reaction
intermediate
adsorption
energies
started
to
coin
fields
heterogeneous
and
electrocatalysis
as
a
blessing
curse
at
same
time.
established
possibility
construct
activity
volcano
plots
function
single
or
two
readily
accessible
descriptors,
but
also
limited
maximal
catalytic
conversion
rate.
In
this
work,
it
is
found
that
these
energy-based
descriptor
spaces
are
not
applicable
electrochemistry,
because
they
lacking
an
important
additional
dimension,
potential
zero
charge.
This
extra
dimension
arises
from
interaction
electric
double
layer
with
intermediates
which
does
scale
energies.
At
example
electrochemical
reduction
CO
2
shown
addition
breaks
relations,
opening
up
huge
chemical
space
via
charge-based
material
design.
The
charge
explains
product
selectivity
trends
in
close
agreement
reported
experimental
data
highlighting
its
importance
for
electrocatalyst
Chemical Science,
Год журнала:
2024,
Номер
15(21), С. 7870 - 7907
Опубликована: Янв. 1, 2024
This
review
highlights
the
structure–activity
relationship
of
ECO
2
RR,
provides
a
detailed
summary
advanced
materials
by
analyzing
electrocatalytic
applications
and
reaction
mechanisms,
discusses
challenges
in
both
devices.
Advanced Energy Materials,
Год журнала:
2023,
Номер
13(27)
Опубликована: Апрель 27, 2023
Abstract
Electrolytes
have
a
profound
impact
on
the
chemical
environment
of
electrocatalysis,
influencing
reaction
rate
and
selectivity
products.
Experimental
theoretical
studies
extensively
investigated
interaction
mechanisms
between
electrolyte
ions
(i.e.,
alkali
metal
cations,
carbonate
anions)
reactants
or
catalyst
surface
in
electrocatalytic
reactions
such
as
hydrogen
evolution
reaction,
oxygen
reduction
water
oxidation
CO
2
reaction.
Past
demonstrated
noticeable
dependence
electrochemical
activity
identity
ions.
However,
few
overviews
comprehensively
specifically
discussed
effects
cations
anions
common
reactions.
In
order
to
clarify
give
more
insights
this
research
area,
review
aims
summarize
highlight
recent
progress
understanding
various
ionic
species
their
influence
diverse
for
splitting,
H
O
production,
reduction.
The
challenges
perspectives
effect
electrocatalysis
are
also
presented.
Chemical Society Reviews,
Год журнала:
2023,
Номер
52(11), С. 3627 - 3662
Опубликована: Янв. 1, 2023
The
selective
methanation
of
CO2
is
an
important
research
area
to
meet
the
net-zero
emission
targets.
Furthermore,
it
crucial
develop
solutions
achieve
carbon
neutrality,
hydrogen
utilization,
circularity,
and
chemical-energy
storage.
This
conversion
can
be
realized
via
thermocatalytic
multistep
power-to-X
route
or
by
direct
electro-
(or
photoelectro)-catalytic
technologies.
Herein,
we
discuss
need
accelerate
Improving
these
technologies
requires
a
better
understanding
catalytic
chemistry
complexity
aspects
consider
in
bridging
electrocatalytic
methanation.
In
this
tutorial
review,
initially
analyze
fundamental
question
competitive
adsorption
key
reactants
regulation
strategies
promote
overall
reaction.
Then,
approach
used
guide
reader
differences
between
thermocatalysis
electrocatalysis.
Finally,
necessary
include
modelling
designing
next-generation
electrocatalysts
for
analyzed.
Hydrogen,
Год журнала:
2023,
Номер
4(4), С. 776 - 806
Опубликована: Окт. 13, 2023
Amid
global
energy
challenges,
the
hydrogen
evolution
reaction
(HER)
is
gaining
traction
for
green
production.
While
catalyst
research
ongoing,
recognizing
electrolyte
effects
remains
crucial
sustainable
production
via
renewable-powered
water
electrolysis.
This
review
delves
into
intricate
of
electrolytes
on
kinetics
HER.
It
examines
key
factors
including
pH,
cations,
anions,
impurities,
and
concentration.
discusses
notion
that
pH
alters
catalyst–electrolyte
interactions
proton
concentrations,
thereby
influencing
such
as
binding
energy,
adsorption,
overall
kinetics.
Moreover,
this
provides
a
briefing
cations
Li+
can
impact
HER
positively
or
negatively,
offering
opportunities
improvement
based
metal
substrate.
Interestingly,
there
potential
be
tuned
using
ions
to
modify
M–H
bond
demonstrating
flexibility
beyond
levels
counter-ions.
The
varied
adsorption
energies
electrodes
are
also
found
influence
anions
impurities
discussed,
emphasizing
both
positive
negative
impacts
it
pointed
out
electrolyte-engineering
approach
enhances
without
permanent
surface
modifications.
underscores
importance
composition,
highlighting
challenges
solutions
in
advancing
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(8), С. 5242 - 5251
Опубликована: Фев. 13, 2024
A
considerable
carbon
loss
of
CO2
electroreduction
in
neutral
and
alkaline
media
severely
limits
its
industrial
viability
as
a
result
the
homogeneous
reaction
OH–
under
interfacial
alkalinity.
Here,
to
mitigate
reactions,
we
conducted
mildly
acidic
media.
By
modulating
environment
via
multiple
electrolyte
effects,
parasitic
hydrogen
evolution
is
suppressed,
leading
faradaic
efficiency
over
80%
for
CO
on
planar
Au
electrode.
Using
rotating
ring-disk
electrode
technique,
ring
constitutes
an
situ
collector
pH
sensor,
enabling
recording
Faradaic
monitoring
while
reduction
takes
place
disk.
The
dominant
branch
switches
from
proton
water
changes
alkaline.
comparison,
starts
within
region
approaches
near-neutral
conditions.
Thereafter,
decays,
place,
protons
are
increasingly
consumed
by
electrogenerated
reduction.
reaches
maximum
just
before
initiates.
Slowing
mass
transport
lowers
current,
hardly
influenced.
In
contrast,
appropriate
protic
anion,
e.g.,
HSO4–
our
case,
weakly
hydrated
cations,
K+,
accelerate
reduction,
with
former
providing
extra
flux
but
higher
local
pH,
latter
stabilizing
*CO2–
intermediate.
ACS Nano,
Год журнала:
2024,
Номер
18(14), С. 9823 - 9851
Опубликована: Март 28, 2024
With
the
increasingly
serious
greenhouse
effect,
electrochemical
carbon
dioxide
reduction
reaction
(CO2RR)
has
garnered
widespread
attention
as
it
is
capable
of
leveraging
renewable
energy
to
convert
CO2
into
value-added
chemicals
and
fuels.
However,
performance
CO2RR
can
hardly
meet
expectations
because
diverse
intermediates
complicated
processes,
necessitating
exploitation
highly
efficient
catalysts.
In
recent
years,
with
advanced
characterization
technologies
theoretical
simulations,
exploration
catalytic
mechanisms
gradually
deepened
electronic
structure
catalysts
their
interactions
intermediates,
which
serve
a
bridge
facilitate
deeper
comprehension
structure-performance
relationships.
Transition
metal-based
(TMCs),
extensively
applied
in
CO2RR,
demonstrate
substantial
potential
for
further
modulation,
given
abundance
d
electrons.
Herein,
we
discuss
representative
feasible
strategies
modulate
catalysts,
including
doping,
vacancy,
alloying,
heterostructure,
strain,
phase
engineering.
These
approaches
profoundly
alter
inherent
properties
TMCs
interaction
thereby
greatly
affecting
rate
pathway
CO2RR.
It
believed
that
rational
design
modulation
fundamentally
provide
viable
directions
development
toward
conversion
many
other
small
molecules.