Abstract
Copper‐based
bimetallic
heterojunction
catalysts
facilitate
the
deep
electrochemical
reduction
of
CO
2
(eCO
RR)
to
produce
high‐value‐added
organic
compounds,
which
hold
significant
promise.
Understanding
influence
copper
interactions
with
other
metals
on
adsorption
strength
various
intermediates
is
crucial
as
it
directly
impacts
reaction
selectivity.
In
this
review,
an
overview
formation
mechanism
catalytic
products
in
eCO
RR
provided
and
highlight
uniqueness
copper‐based
catalysts.
By
considering
different
metals'
tendencies
toward
intermediates,
are
classified,
including
copper,
into
four
categories.
The
significance
advantages
constructing
then
discussed
delve
research
findings
current
development
status
types
Finally,
insights
offered
design
strategies
for
future
high‐performance
electrocatalysts,
aiming
contribute
multi‐carbon
fuels
high
Oxide-derived
copper
(OD-Cu)
is
the
most
efficient
and
likely
practical
electrocatalyst
for
CO
2
reduction
toward
multicarbon
products.
However,
inevitable
but
poorly
understood
reconstruction
from
pristine
state
to
working
of
OD-Cu
under
strong
conditions
largely
hinders
rational
construction
catalysts
products,
especially
C
3
products
like
n-propanol.
Here,
we
simulate
CuO
Cu
O
into
their
derived
by
molecular
dynamics,
revealing
that
CuO-derived
(CuOD-Cu)
intrinsically
has
a
richer
population
undercoordinated
sites
higher
surficial
atom
density
than
counterpart
O-derived
(Cu
OD-Cu)
because
vigorous
oxygen
removal.
In
situ
spectroscopes
disclose
coordination
number
CuOD-Cu
considerably
lower
OD-Cu,
enabling
fast
kinetics
reaction
strengthened
binding
*C
intermediate(s).
Benefiting
rich
sites,
achieves
remarkable
n-propanol
faradaic
efficiency
up
~17.9%,
whereas
dominantly
generates
formate.
ACS Catalysis,
Год журнала:
2023,
Номер
13(21), С. 14163 - 14172
Опубликована: Окт. 20, 2023
Polyethylene
terephthalate
(PET)
plastic
and
CO2
pollution
have
seriously
threatened
the
ecological
environment
caused
a
huge
waste
of
carbon
resources.
Herein,
we
report
an
electrocatalytic
waste-treating-waste
strategy
for
concurrently
upgrading
PET
wastes
into
value-added
formic
acid
(HCOOH),
in
which
both
anode
(oxygen-vacancy-rich
Ni(OH)2-VO)
cathode
(Bi/Bi2O3
heterostructure)
electrocatalysts
were
elaborately
designed
from
derivatives.
Impressively,
as-prepared
Ni(OH)2-VO
Bi/Bi2O3
achieve
high
selectivity
HCOOH
(86
91%,
respectively)
with
industrial-level
current
densities
at
ultralow
potentials
(300
mA
cm–2
1.6
V
−272
−1.4
V,
respectively).
Further
experimental
theoretical
results
reveal
that
abundant
oxygen
vacancies
will
largely
facilitate
formation
Ni3+
species
accelerate
subsequent
processes
dehydrogenation
C–C
bond
breakage
during
upcycling.
Meanwhile,
interface
electron
transfer
Bi2O3
to
Bi
benefits
keeping
valence
sites
optimizes
adsorption
OCHO*
intermediate,
thereby
endowing
efficient
performance
toward
reduction
HCOOH.
As
proof
concept,
solar-powered
flow
reactor
real-time
monitoring
control
functions
was
designed,
realized
record
Faradaic
efficiency
181%
This
work
offers
opportunities
utilization
provides
constructive
guidance
design
advanced
converting
valuable
chemicals.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(20), С. 14260 - 14266
Опубликована: Май 7, 2024
The
electrochemical
CO2
reduction
reaction
by
copper-based
catalysts
features
a
promising
approach
to
generate
value-added
multicarbon
(C2+)
products.
However,
due
the
unfavored
formation
of
oxygenate
intermediates
on
catalyst
surface,
selectivity
C2+
alcohols
like
ethanol
remains
unsatisfactory
compared
that
ethylene.
bifurcation
point
(i.e.,
CH2═CHO*
intermediate
adsorbed
Cu
via
Cu–O–C
linkage)
is
critical
product
selectivity,
whereas
subsequent
cleavage
Cu–O
or
O–C
bond
determines
ethylene
pathway.
Inspired
hard–soft
acid–base
theory,
in
this
work,
we
demonstrate
an
electron
delocalization
tuning
strategy
nitrene
surface
functionalization
approach,
which
allows
weakening
and
cleaving
CH2═CHO*,
as
well
accelerating
hydrogenation
C═C
along
As
result,
nitrene-functionalized
exhibited
much-enhanced
Faradaic
efficiency
45%
with
peak
partial
current
density
406
mA·cm–2,
substantially
exceeding
unmodified
amide-functionalized
Cu.
When
assembled
membrane
electrode
assembly
electrolyzer,
presented
stable
CO2-to-ethanol
conversion
for
>300
h
at
industrial
400
mA·cm–2.
In
current
research,
achieving
carbon
neutrality
has
become
a
primary
focus
through
the
utilization
of
various
conversion
technologies
that
transform
dioxide
(CO
2
)
into
valuable
chemicals
or
fuels.
Covalent
organic
frameworks
(COFs),
as
emerging
crystalline
polymers,
offer
distinct
advantages
in
CO
compared
to
other
materials.
These
include
controllable
nanoscale
pores,
predefined
functional
units,
editable
framework
structures,
and
rich
conjugated
systems.
The
unique
characteristics
COFs
make
them
highly
promising
electrocatalysts
for
conversion.
This
review
provides
comprehensive
overview
pioneering
works
recent
research
on
COF‐based
materials
electrochemical
reduction
reaction.
offers
analysis
design
principles
reactive
sites,
skeleton
pore
functionalities,
3D
frameworks,
morphologies,
composite
COFs,
aiming
enhance
electrocatalysis.
Finally,
this
presents
some
recommendations
material
design,
reaction
mechanisms,
theoretical
computations
understanding
mechanisms
further
facilitate
high‐performance
electrocatalysts.
Abstract
Rising
carbon
dioxide
(CO
2
)
levels
in
the
atmosphere
are
recognized
as
a
threat
to
atmospheric
stability
and
life.
Although
this
greenhouse
gas
is
being
produced
on
large
scale,
there
solutions
reduction
indeed
utilization
of
gas.
Many
these
involve
costly
or
unstable
technologies,
such
air‐sensitive
metal–organic
frameworks
(MOFs)
for
CO
capture
“non‐green”
systems
amine
scrubbing.
Conjugated
microporous
polymers
(CMPs)
represent
simpler,
cheaper,
greener
solution
utilization.
They
often
easy
synthesize
at
scale
(a
one
pot
reaction
many
cases),
chemically
thermally
stable
(especially
comparison
with
their
MOF
covalent
organic
framework
(COF)
counterparts,
owing
amorphous
nature),
and,
result,
cheap
manufacture.
Furthermore,
surface
areas,
tunable
porous
chemical
structures
mean
they
reported
highly
efficient
motifs.
In
addition,
provide
dual
pathway
utilize
captured
via
conversion
electrochemical
into
industrially
valuable
products.
Recent
studies
show
that
all
attractive
properties
can
be
realized
metal‐free
CMPs,
presenting
truly
green
option.
The
promising
results
two
fields
CMP
applications
reviewed
explored
here.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(25), С. 16950 - 16962
Опубликована: Июнь 4, 2024
Nowadays,
plastic
waste
threatens
public
health
and
the
natural
ecosystems
of
our
lives.
It
is
highly
beneficial
to
recycle
in
order
maximize
reuse
its
contained
carbon
sources
for
development
other
valuable
products.
Unfortunately,
traditional
techniques
usually
require
significant
energy
consumption
result
generation
hazardous
waste.
Herein,
up-to-date
developments
on
"green"
strategies
under
mild
conditions
including
electrocatalysis,
photocatalysis,
photoelectrocatalysis
wastes
are
presented.
During
oxidation
plastics
these
strategies,
corresponding
reduction
reactions
exist,
which
affect
property
catalytic
conversion.
Particularly,
we
mainly
focus
how
design
half
reactions,
such
as
water
reduction,
dioxide
nitrate
reduction.
Finally,
provide
forward-looking
insight
into
enhancement
extension
more
organic
catalysis,
a
comprehensive
exploration
underlying
mechanisms
through
situ
studies
theoretical
analysis
problems
practical
applications
that
needs
be
solved.
