Nature Catalysis,
Journal Year:
2022,
Volume and Issue:
5(4), P. 259 - 267
Published: April 21, 2022
Abstract
Convoluted
selectivity
trends
and
a
missing
link
between
reaction
product
distribution
catalyst
properties
hinder
practical
applications
of
the
electrochemical
CO
2
reduction
(CO
RR)
for
multicarbon
generation.
Here
we
employ
operando
X-ray
absorption
diffraction
methods
with
subsecond
time
resolution
to
unveil
surprising
complexity
catalysts
exposed
dynamic
conditions.
We
show
that
by
using
pulsed
protocol
consisting
alternating
working
oxidizing
potential
periods
dynamically
perturb
derived
from
Cu
O
nanocubes,
one
can
decouple
effect
ensemble
coexisting
copper
species
on
distribution.
In
particular,
an
optimized
balance
oxidized
reduced
surface
achieved
within
narrow
range
cathodic
anodic
pulse
durations
resulted
in
twofold
increase
ethanol
production
compared
static
RR
This
work
thus
prepares
ground
steering
through
controlled
structural
chemical
transformations.
Nature Communications,
Journal Year:
2021,
Volume and Issue:
12(1)
Published: March 11, 2021
Abstract
Electrochemical
CO
2
reduction
can
produce
valuable
products
with
high
energy
densities
but
the
process
is
plagued
by
poor
selectivities
and
low
yields.
Propanol
represents
a
challenging
product
to
obtain
due
complicated
C
3
forming
mechanism
that
requires
both
stabilization
of
*C
intermediates
subsequent
1
–C
coupling.
Herein,
density
function
theory
calculations
revealed
double
sulfur
vacancies
formed
on
hexagonal
copper
sulfide
feature
as
efficient
electrocatalytic
centers
for
stabilizing
CO*
OCCO*
dimer,
further
CO–OCCO
coupling
form
species,
which
cannot
be
realized
CuS
single
or
no
vacancies.
The
were
then
experimentally
synthesized
an
electrochemical
lithium
tuning
strategy,
during
was
well-tuned
charge/discharge
cycle
number.
vacancy-rich
catalyst
exhibited
Faradaic
efficiency
toward
n-propanol
15.4
±
1%
at
−1.05
V
versus
reversible
hydrogen
electrode
in
H-cells,
partial
current
9.9
mA
cm
−2
−0.85
flow-cells,
comparable
best
reported
n-propanol.
Our
work
suggests
attractive
approach
create
anion
vacancy
pairs
catalytic
multi-carbon-products.
ACS Nano,
Journal Year:
2021,
Volume and Issue:
15(5), P. 7975 - 8000
Published: May 6, 2021
Electrochemical
CO2
reduction
to
value-added
chemicals
and
fuels
is
a
promising
approach
mitigate
the
greenhouse
effect
arising
from
anthropogenic
emission
energy
shortage
caused
by
depletion
of
nonrenewable
fossil
fuels.
The
generation
multicarbon
(C2+)
products,
especially
hydrocarbons
oxygenates,
great
interest
for
industrial
applications.
To
date,
Cu
only
metal
known
catalyze
C–C
coupling
in
electrochemical
reaction
(eCO2RR)
with
appreciable
efficiency
kinetic
viability
produce
wide
range
C2
products
aqueous
solutions.
Nonetheless,
poor
product
selectivity
associated
main
technical
problem
application
eCO2RR
technology
on
global
scale.
Based
extensive
research
efforts,
delicate
rational
design
electrocatalyst
architecture
using
principles
nanotechnology
likely
significantly
affect
adsorption
energetics
some
key
intermediates
hence
inherent
pathways.
In
this
review,
we
summarize
recent
progress
that
has
been
achieved
tailoring
efficient
conversion
target
products.
By
considering
experimental
computational
results,
further
analyze
underlying
correlations
between
catalyst
its
toward
Finally,
major
challenges
are
outlined,
directions
future
development
suggested.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(33), P. 18178 - 18184
Published: July 9, 2021
Abstract
Monitoring
and
controlling
the
reconstruction
of
materials
under
working
conditions
is
crucial
for
precise
identification
active
sites,
elucidation
reaction
mechanisms,
rational
design
advanced
catalysts.
Herein,
a
Bi‐based
metal–organic
framework
(Bi‐MOF)
electrochemical
CO
2
reduction
selected
as
case
study.
In
situ
Raman
spectra
combined
with
ex
electron
microscopy
reveal
that
intricate
Bi‐MOF
can
be
controlled
using
two
steps:
1)
electrolyte‐mediated
dissociation
conversion
to
Bi
O
3
,
2)
potential‐mediated
Bi.
The
intentionally
reconstructed
catalyst
exhibits
excellent
activity,
selectivity,
durability
formate
production,
unsaturated
surface
atoms
formed
during
become
sites.
This
work
emphasizes
significant
impact
pre‐catalyst
provides
insight
into
highly
stable
electrocatalysts
through
regulation
these
processes.
Advanced Materials,
Journal Year:
2021,
Volume and Issue:
33(38)
Published: July 31, 2021
Abstract
The
objective
of
photocatalytic
CO
2
reduction
(PCR)
is
to
achieve
high
selectivity
for
a
single
energy‐bearing
product
with
efficiency
and
stability.
bulk
configuration
usually
determines
charge
carrier
kinetics,
whereas
surface
atomic
arrangement
defines
the
PCR
thermodynamic
pathway.
Concurrent
engineering
structures
therefore
crucial
achieving
goal
PCR.
Herein,
an
ultrastable
highly
selective
using
homogeneously
doped
BiOCl
nanosheets
synthesized
via
inventive
molten
strategy
presented.
With
B
O
3
as
both
salt
doping
precursor,
this
new
approach
ensures
boron
(B)
from
into
dual
functionalities.
Bulk
mitigates
strong
excitonic
effects
confined
in
2D
by
significantly
reducing
exciton
binding
energies,
surface‐doped
atoms
reconstruct
extracting
lattice
hydroxyl
groups,
resulting
intimate
B‐oxygen
vacancy
(B‐OV)
associates.
These
exclusive
B‐OV
associates
enable
spontaneous
activation,
suppress
competitive
hydrogen
evolution
promote
proton‐coupled
electron
transfer
step
stabilizing
*COOH
generation.
As
result,
homogeneous
B‐doped
exhibit
98%
‐to‐CO
under
visible
light,
impressive
rate
83.64
µmol
g
−1
h
ultrastability
long‐term
testing
120
h.