Nature Communications,
Год журнала:
2021,
Номер
12(1)
Опубликована: Сен. 1, 2021
Abstract
Electrochemical
reduction
of
CO
2
(CO
R)
to
formic
acid
upgrades
waste
;
however,
up
now,
chemical
and
structural
changes
the
electrocatalyst
have
often
led
deterioration
performance
over
time.
Here,
we
find
that
alloying
p-block
elements
with
differing
electronegativities
modulates
redox
potential
active
sites
stabilizes
them
throughout
extended
R
operation.
Active
Sn-Bi/SnO
surfaces
formed
in
situ
on
homogeneously
alloyed
Bi
0.1
Sn
crystals
stabilize
R-to-formate
pathway
2400
h
(100
days)
continuous
operation
at
a
current
density
100
mA
cm
−2
.
This
is
accompanied
by
Faradaic
efficiency
95%
an
overpotential
~
−0.65
V.
Operating
experimental
studies
as
well
computational
investigations
show
stabilized
offer
near-optimal
binding
energy
key
formate
intermediate
*OCHO.
Using
cation-exchange
membrane
electrode
assembly
device,
demonstrate
stable
production
concentrated
HCOO
–
solution
(3.4
molar,
15
wt%)
h.
Advanced Energy Materials,
Год журнала:
2019,
Номер
10(11)
Опубликована: Дек. 20, 2019
Abstract
Carbon‐based
heteroatom‐coordinated
single‐atom
catalysts
(SACs)
are
promising
candidates
for
energy‐related
electrocatalysts
because
of
their
low‐cost,
tunable
catalytic
activity/selectivity,
and
relatively
homogeneous
morphologies.
Unique
interactions
between
single
metal
sites
surrounding
coordination
environments
play
a
significant
role
in
modulating
the
electronic
structure
centers,
leading
to
unusual
scaling
relationships,
new
reaction
mechanisms,
improved
performance.
This
review
summarizes
recent
advancements
engineering
local
environment
SACs
electrocatalytic
performance
several
crucial
energy‐convention
electrochemical
reactions:
oxygen
reduction
reaction,
hydrogen
evolution
CO
2
nitrogen
reaction.
Various
strategies
including
heteroatom‐doping,
changing
location
on
support,
introducing
external
ligands,
constructing
dual
comprehensively
discussed.
The
controllable
synthetic
methods
activity
enhancement
mechanism
state‐of‐the‐art
also
highlighted.
Recent
achievements
modification
will
provide
an
understanding
structure–activity
relationship
rational
design
advanced
electrocatalysts.
Chemical Society Reviews,
Год журнала:
2020,
Номер
49(18), С. 6632 - 6665
Опубликована: Янв. 1, 2020
The
electrochemical
reduction
of
CO2
stores
intermittent
renewable
energy
in
valuable
raw
materials,
such
as
chemicals
and
transportation
fuels,
while
minimizing
carbon
emissions
promoting
carbon-neutral
cycles.
Recent
technoeconomic
reports
suggested
economically
feasible
target
products
electroreduction
the
relative
influence
key
performance
parameters
faradaic
efficiency
(FE),
current
density,
overpotential
practical
industrial-scale
applications.
Furthermore,
fundamental
factors,
available
reaction
pathways,
shared
intermediates,
competing
hydrogen
evolution
reaction,
scaling
relations
intermediate
binding
energies,
mass
transport
limitations,
should
be
considered
relation
to
performance.
Intensive
research
efforts
have
been
devoted
designing
developing
advanced
electrocatalysts
improving
mechanistic
understanding.
More
recently,
focus
was
extended
catalyst
environment,
because
interfacial
region
can
delicately
modulate
catalytic
activity
provide
effective
solutions
challenges
that
were
not
fully
addressed
material
development
studies.
Herein,
we
discuss
importance
catalyst-electrolyte
interfaces
operational
based
on
kinetic
equations.
extensively
review
previous
studies
controlling
organic
modulators,
electrolyte
ions,
electrode
structures,
well
three-phase
boundary
at
interface.
modulates
electrocatalytic
properties
via
electronic
modification,
stabilization,
proton
delivery
regulation,
structure
reactant
concentration
control,
regulation.
We
understanding
interface
its
effect
activity.
Advanced Energy Materials,
Год журнала:
2020,
Номер
10(38)
Опубликована: Авг. 13, 2020
Abstract
Electrocatalysis
plays
a
critical
role
in
clean
energy
conversion,
enabling
great
improvement
for
future
sustainable
technologies.
Single
atom
catalysts
(SACs)
derived
from
metal–organic
framework
(MOF)
are
emerging
extraordinary
materials
electrochemical
catalytic
applications.
Covering
the
merits
of
unique
electronic
structure,
low‐coordination
environment,
quantum
size
effect,
and
metal–support
interaction,
SACs
promise
enhanced
electrocatalytic
activity,
stability,
selectivity
field
conversion.
In
this
article,
MOF
synthesis
routes
to
afford
well‐dispersed
along
with
respective
mechanism
systematically
reviewed
first,
typical
examples
each
strategy
carefully
discussed.
Then
characterization
techniques
understanding
isolated
spatial
distribution,
local
coordination
environment
SACs,
insights
into
stable
mechanisms
provided
by
density
functional
theory
(DFT)
calculations
summarized.
addition,
several
important
applications
MOF‐derived
including
oxygen
reduction
reaction,
CO
2
nitrogen
hydrogen
evolution
etc.,
highlighted.
To
facilitate
development
high‐performing
technical
challenges
corresponding
research
directions
proposed.
Energy & Environmental Science,
Год журнала:
2020,
Номер
13(8), С. 2275 - 2309
Опубликована: Янв. 1, 2020
This
review
discusses
how
morphology
and
interface
engineering
promote
electrocatalytic
CO2
reduction,
providing
general
design
principles
to
fabricate
advanced
electrode
catalysts.
Chemical Society Reviews,
Год журнала:
2021,
Номер
50(21), С. 11785 - 11843
Опубликована: Янв. 1, 2021
Since
the
discovery
of
N-doped
carbon
nanotubes
as
first
carbon-based
metal-free
electrocatalyst
(C-MFEC)
for
oxygen
reduction
reaction
(ORR)
in
2009,
C-MFECs
have
shown
multifunctional
electrocatalytic
activities
many
reactions
beyond
ORR,
such
evolution
(OER),
hydrogen
(HER),
dioxide
(CO2RR),
nitrogen
(NRR),
and
peroxide
production
(H2O2PR).
Consequently,
attracted
a
great
deal
interest
various
applications,
including
metal-air
batteries,
water
splitting
devices,
regenerative
fuel
cells,
solar
chemical
production,
purification,
to
mention
few.
By
altering
electronic
configuration
and/or
modulating
their
spin
angular
momentum,
both
heteroatom(s)
doping
structural
defects
(e.g.,
atomic
vacancy,
edge)
been
demonstrated
create
catalytic
active
sites
skeleton
graphitic
materials.
Although
certain
made
be
comparable
or
even
better
than
counterparts
based
on
noble
metals,
transition
metals
hybrids,
further
research
development
are
necessary
order
translate
practical
applications.
In
this
article,
we
present
timely
comprehensive,
but
critical,
review
recent
advancements
field
within
past
five
years
so
by
discussing
types
catalyzed
C-MFECs.
An
emphasis
is
given
potential
applications
energy
conversion
storage.
The
structure-property
relationship
mechanistic
understanding
will
also
discussed,
along
with
current
challenges
future
perspectives.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
144(1), С. 259 - 269
Опубликована: Дек. 28, 2021
The
electrosynthesis
of
valuable
multicarbon
chemicals
using
carbon
dioxide
(CO2)
as
a
feedstock
has
substantially
progressed
recently
but
still
faces
considerable
challenges.
A
major
difficulty
lines
in
the
sluggish
kinetics
forming
carbon-carbon
(C-C)
bonds,
especially
neutral
media.
We
report
here
that
oxide-derived
copper
crystals
enclosed
by
six
{100}
and
eight
{111}
facets
can
reduce
CO2
to
products
with
high
Faradaic
efficiency
74.9
±
1.7%
at
commercially
relevant
current
density
300
mA
cm-2
1
M
KHCO3
(pH
∼
8.4).
By
combining
experimental
computational
studies,
we
uncovered
Cu(100)/Cu(111)
interfaces
offer
favorable
local
electronic
structure
enhances
*CO
adsorption
lowers
C-C
coupling
activation
energy
barriers,
performing
superior
Cu(100)
Cu(111)
surfaces,
respectively.
On
this
catalyst,
no
obvious
degradation
was
observed
over
50
h
continuous
operation.
Chemical Society Reviews,
Год журнала:
2020,
Номер
49(21), С. 7488 - 7504
Опубликована: Янв. 1, 2020
Anthropogenic
carbon
dioxide
(CO2)
emissions
contribute
to
the
greenhouse
effect
and
global
warming,
which
can
lead
undesirable
climate
change
extinction
of
species.
Besides
ongoing
efforts
develop
environmentally
benign
sources
energy
advance
technologies
for
capture
sequestration
CO2,
transformation
emitted
CO2
into
valuable
products
is
a
pragmatic
solution
curb
its
accumulation
in
atmosphere.
In
this
regard,
electrochemical
reduction
(ECR)
powered
by
renewable
electricity
provides
an
attractive
approach
because
it
not
only
converts
fuels
chemicals
but
also
offers
long-term
storage
intermittent
energies.
ECR,
gas
diffusion
electrode
(GDE)
most
critical
component
has
been
subject
intensive
research
last
few
years.
This
tutorial
review
insightful
guide
developing
GDEs
with
high
activity,
selectivity,
stability,
three
important
performance
metrics
ECR.
First,
we
introduce
fundamentals
including
chemical
physical
phenomena
at
electrodes
as
well
cell
configurations.
Next,
discuss
recent
advances
GDE
design,
focusing
on
their
structure-performance
correlation
fabrication
techniques
each
GDEs.
Finally,
remaining
challenges
propose
promising
directions
design
efficient
aims
promoting
development
industrially
relevant
ECR
systems
bring
technology
practical
applications.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(32), С. 14936 - 14944
Опубликована: Авг. 4, 2022
An
ampere-level
current
density
of
CO2
electrolysis
is
critical
to
realize
the
industrial
production
multicarbon
(C2+)
fuels.
However,
under
such
a
large
density,
poor
CO
intermediate
(*CO)
coverage
on
catalyst
surface
induces
competitive
hydrogen
evolution
reaction,
which
hinders
reduction
reaction
(CO2RR).
Herein,
we
report
reliable
CO2-to-C2+
by
heteroatom
engineering
Cu
catalysts.
The
Cu-based
compounds
with
(N,
P,
S,
O)
are
electrochemically
reduced
heteroatom-derived
significant
structural
reconstruction
CO2RR
conditions.
It
found
that
N-engineered
(N-Cu)
exhibits
best
productivity
remarkable
Faradaic
efficiency
73.7%
-1100
mA
cm-2
and
an
energy
37.2%
-900
cm-2.
Particularly,
it
achieves
C2+
partial
-909
at
-1.15
V
versus
reversible
electrode,
outperforms
most
reported
In
situ
spectroscopy
indicates
adjusts
*CO
adsorption
alters
local
H
proton
consumption
in
solution.
Density
functional
theory
studies
confirm
high
strength
N-Cu
results
from
depressed
HER
promoted
both
bridge
atop
sites
Cu,
greatly
reduces
barrier
for
C-C
coupling.