Nature Communications,
Journal Year:
2019,
Volume and Issue:
10(1)
Published: June 26, 2019
Abstract
Formic
acid
(or
formate)
is
suggested
to
be
one
of
the
most
economically
viable
products
from
electrochemical
carbon
dioxide
reduction.
However,
its
commercial
viability
hinges
on
development
highly
active
and
selective
electrocatalysts.
Here
we
report
that
structural
defects
have
a
profound
positive
impact
electrocatalytic
performance
bismuth.
Bismuth
oxide
double-walled
nanotubes
with
fragmented
surface
are
prepared
as
template,
cathodically
converted
defective
bismuth
nanotubes.
This
electrocatalyst
enables
reduction
formate
excellent
activity,
selectivity
stability.
Most
significantly,
current
density
reaches
~288
mA
cm
−2
at
−0.61
V
versus
reversible
hydrogen
electrode
within
flow
cell
reactor
under
ambient
conditions.
Using
functional
theory
calculations,
activity
rationalized
outcome
abundant
sites
stabilize
*OCHO
intermediate.
Furthermore,
this
coupled
silicon
photocathodes
achieves
high-performance
photoelectrochemical
Chemical Reviews,
Journal Year:
2019,
Volume and Issue:
119(12), P. 7610 - 7672
Published: May 22, 2019
To
date,
copper
is
the
only
heterogeneous
catalyst
that
has
shown
a
propensity
to
produce
valuable
hydrocarbons
and
alcohols,
such
as
ethylene
ethanol,
from
electrochemical
CO2
reduction
(CO2R).
There
are
variety
of
factors
impact
CO2R
activity
selectivity,
including
surface
structure,
morphology,
composition,
choice
electrolyte
ions
pH,
cell
design.
Many
these
often
intertwined,
which
can
complicate
discovery
design
efforts.
Here
we
take
broad
historical
view
different
aspects
their
complex
interplay
in
catalysis
on
Cu,
with
purpose
providing
new
insights,
critical
evaluations,
guidance
field
regard
research
directions
best
practices.
First,
describe
various
experimental
probes
complementary
theoretical
methods
have
been
used
discern
mechanisms
by
products
formed,
next
present
our
current
understanding
reaction
networks
for
Cu.
We
then
analyze
two
key
attempts
alter
selectivity
Cu:
nanostructuring
formation
bimetallic
electrodes.
Finally,
offer
some
perspectives
future
outlook
CO2R.
Science,
Journal Year:
2019,
Volume and Issue:
364(6438)
Published: April 25, 2019
BACKGROUND
As
the
world
continues
to
transition
toward
carbon
emissions–free
energy
technologies,
there
remains
a
need
also
reduce
emissions
of
chemical
production
industry.
Today
many
world’s
chemicals
are
produced
from
fossil
fuel–derived
feedstocks.
Electrochemical
conversion
dioxide
(CO
2
)
into
feedstocks
offers
way
turn
waste
valuable
products,
closing
loop.
When
coupled
renewable
sources
electricity,
these
products
can
be
made
with
net
negative
footprint,
helping
sequester
CO
usable
goods.
Research
and
development
electrocatalytic
materials
for
reduction
has
intensified
in
recent
years,
advances
selectivity,
efficiency,
reaction
rate
progressing
practical
implementation.
A
variety
,
such
as
alcohols,
oxygenates,
synthesis
gas
(syngas),
olefins—staples
global
Because
at
substantial
scale,
switch
renewably
powered
could
result
impact.
The
advancement
electrochemical
technology
convert
electrons
generated
power
stable
form
represents
one
avenue
long-term
(e.g.,
seasonal)
storage
energy.
ADVANCES
science
progress,
priority
given
pinpoint
more
accurately
targets
application,
economics
barriers
market
entry.
It
will
important
scale
electrolyzers
increase
stability
catalysts
thousands
hours
continuous
operation.
Product
separation
efficient
recycling
electrolyte
managed.
petrochemical
industry
operates
massive
complicated
supply
chain
heavy
capital
costs.
Commodity
markets
difficult
penetrate
priced
on
feedstock,
which
is
currently
inexpensive
shale
boom.
capture
costs
flue
or
direct
air
product
unreacted
consider.
Assuming
that
technologies
apace,
what
it
take
disrupt
sector,
society
gain
by
doing
so?
This
review
presents
technoeconomic
assessment
ethylene,
ethanol,
monoxide,
offering
target
figures
merit
application.
price
electricity
far
largest
cost
driver.
begin
match
those
traditional
processes
when
prices
fall
below
4
cents
per
kWh
efficiencies
reach
least
60%.
footprint.
comparative
analysis
electrocatalytic,
biocatalytic,
shows
potential
yield
greatest
emissions,
provided
steady
clean
available.
Additionally,
opportunities
exist
combine
range
other
thermo-
biocatalytic
slowly
electrify
existing
further
upgrade
useful
chemicals.
Technical
challenges
operating
lifetime,
discussed.
Supply
management
entrenched
industrial
competition
considered.
OUTLOOK
There
exists
increasingly
widespread
recognition
means
production.
pricing
mechanisms
being
developed
seeing
increased
governmental
support.
nascent
utilization
economy
gaining
traction,
startup
companies,
prizes,
research
efforts
all
pursuing
new
technologies.
Recent
through
use
diffusion
electrodes
pushing
current
densities
selectivities
realm
use.
Despite
this
remain
technical
must
overcome
commercial
ultimately
decide
whether
experiences
conversion.
Reduction
using
sourced
transform
commodity
fuels.
Science,
Journal Year:
2020,
Volume and Issue:
367(6478), P. 661 - 666
Published: Feb. 6, 2020
Electrolysis
offers
an
attractive
route
to
upgrade
greenhouse
gases
such
as
carbon
dioxide
(CO2)
valuable
fuels
and
feedstocks;
however,
productivity
is
often
limited
by
gas
diffusion
through
a
liquid
electrolyte
the
surface
of
catalyst.
Here,
we
present
catalyst:ionomer
bulk
heterojunction
(CIBH)
architecture
that
decouples
gas,
ion,
electron
transport.
The
CIBH
comprises
metal
superfine
ionomer
layer
with
hydrophobic
hydrophilic
functionalities
extend
ion
transport
from
tens
nanometers
micrometer
scale.
By
applying
this
design
strategy,
achieved
CO2
electroreduction
on
copper
in
7
M
potassium
hydroxide
(pH
≈
15)
ethylene
partial
current
density
1.3
amperes
per
square
centimeter
at
45%
cathodic
energy
efficiency.
Advanced Materials,
Journal Year:
2019,
Volume and Issue:
31(31)
Published: May 16, 2019
The
electrochemical
reduction
of
CO2
is
a
promising
route
to
convert
intermittent
renewable
energy
storable
fuels
and
valuable
chemical
feedstocks.
To
scale
this
technology
for
industrial
implementation,
deepened
understanding
how
the
reaction
(CO2
RR)
proceeds
will
help
converge
on
optimal
operating
parameters.
Here,
techno-economic
analysis
presented
with
goal
identifying
maximally
profitable
products
performance
targets
that
must
be
met
ensure
economic
viability-metrics
include
current
density,
Faradaic
efficiency,
stability.
latest
computational
RR
discussed
along
can
contribute
rational
design
efficient,
selective,
stable
electrocatalysts.
Catalyst
materials
are
classified
according
their
selectivity
interest
potential
achieve
assessed.
recent
progress
opportunities
in
system
electroreduction
described.
conclude,
remaining
technological
challenges
highlighted,
suggesting
full-cell
efficiency
as
guiding
metric
impact.