ACS Catalysis,
Год журнала:
2023,
Номер
13(7), С. 5033 - 5042
Опубликована: Март 29, 2023
Electrocatalytic
CO2
reduction
has
been
considered
an
effective
carbon
neutrality
as
well
energy
storage
strategy
integrated
with
renewable
electricity.
conversion
to
formate
is
a
feasible
route
using
earth-abundant
and
nontoxic
tin-based
catalysts.
However,
they
suffer
from
degradation
thus
decrease
in
selectivity
during
operation.
Guided
by
density
functional
theory
(DFT)
calculations,
herein,
we
synthesized
CeO2–SnO2
heterostructures
facile
electrospinning
method,
which
exhibited
maximum
partial
current
of
∼500
mA·cm–2
87.1%
faradaic
efficiency
long-term
stability
flow
cell.
Proved
situ
attenuated
total
reflectance
infrared
absorption
spectroscopy
(ATR-IRAS)
Raman
spectra
post-X-ray
photoelectron
(XPS)
analysis,
dynamic
CeO2-mediated
Sn0/Snδ+
redox
cycle
mechanism
was
proposed:
oxygen
vacancies
generated
on
cerium
oxides
prompted
water
dissociation
produce
*OH
*H
species,
where
the
former
oxidize
Sn0
into
active
Snδ+,
facilitating
key
intermediate
*OCHO
help
latter.
This
work
may
provide
general
design
stable
efficient
catalysts
for
practical
electrolyzers.
Advanced Materials,
Год журнала:
2022,
Номер
34(23)
Опубликована: Март 9, 2022
Abstract
2D
materials
show
many
particular
properties,
such
as
high
surface‐to‐volume
ratio,
anisotropic
degree,
and
adjustable
chemical
functionality.
These
unique
properties
in
have
sparked
immense
interest
due
to
their
applications
photocatalytic
systems,
resulting
significantly
enhanced
light
capture,
charge‐transfer
kinetics,
surface
reaction.
Herein,
the
research
progress
photocatalysts
based
on
varied
compositions
functions,
followed
by
specific
modification
strategies,
is
introduced.
Fundamental
principles
focusing
harvesting,
charge
separation,
molecular
adsorption/activation
2D‐material‐based
system
are
systemically
explored.
The
examples
described
here
detail
use
of
various
energy‐conversion
including
water
splitting,
carbon
dioxide
reduction,
nitrogen
fixation,
hydrogen
peroxide
production,
organic
synthesis.
Finally,
elaborating
challenges
possible
solutions
for
developing
these
materials,
review
expected
provide
some
inspiration
future
used
efficient
energy
conversions.
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.
Deleted Journal,
Год журнала:
2022,
Номер
1, С. e9120009 - e9120009
Опубликована: Май 26, 2022
With
the
increasing
demand
for
fuel
causing
serious
environmental
pollution,
it
is
urgent
to
develop
new
and
environmentally
friendly
energy
conversion
devices.
These
devices,
however,
require
good,
inexpensive
materials
electrodes
so
on.
The
multifunctional
properties
of
porphyrins
enable
framework
(e.g.,
metal-organic
frameworks
covalent
organic
frameworks)
be
applied
in
devices
due
their
simple
synthesis,
high
chemical
stability,
abundant
metallic
active
sites,
adjustable
crystalline
structure
specific
surface
area.
Herein,
types
porphyrin
structural
blocks
are
briefly
reviewed.
They
can
used
as
ligands
or
directly
assembled
with
generate
high-performance
electro-/photo-catalysts.
catalysts
electro-/photo-catalytic
water
splitting,
carbon
dioxide
reduction,
electrocatalytic
oxygen
reduction
also
summarized
introduced.
At
end
article,
we
present
challenges
porphyrin-based
above
application
corresponding
solutions.
We
expect
flourish
coming
years.
Advanced Materials,
Год журнала:
2023,
Номер
35(18)
Опубликована: Фев. 6, 2023
Electrocatalytic
CN
coupling
between
carbon
dioxide
and
nitrate
has
emerged
to
meet
the
comprehensive
demands
of
footprint
closing,
valorization
waste,
sustainable
manufacture
urea.
However,
identification
catalytic
active
sites
design
efficient
electrocatalysts
remain
a
challenge.
Herein,
synthesis
urea
catalyzed
by
copper
single
atoms
decorated
on
CeO2
support
(denoted
as
Cu1
-CeO2
)
is
reported.
The
catalyst
exhibits
an
average
yield
rate
52.84
mmol
h-1
gcat.-1
at
-1.6
V
versus
reversible
hydrogen
electrode.
Operando
X-ray
absorption
spectra
demonstrate
reconstitution
(Cu1
clusters
(Cu4
during
electrolysis.
These
electrochemically
reconstituted
Cu4
are
real
for
electrocatalytic
synthesis.
Favorable
reactions
formation
validated
using
operando
synchrotron-radiation
Fourier
transform
infrared
spectroscopy
theoretical
calculations.
Dynamic
transformations
single-atom
configurations
occur
when
applied
potential
switched
open-circuit
potential,
endowing
with
superior
structural
electrochemical
stabilities.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(12), С. 6622 - 6627
Опубликована: Март 20, 2023
Copper
(Cu)
can
efficiently
catalyze
the
electrochemical
CO2
reduction
reaction
(CO2RR)
to
produce
value-added
fuels
and
chemicals,
among
which
methane
(CH4)
has
drawn
attention
due
its
high
mass
energy
density.
However,
linear
scaling
relationship
between
adsorption
energies
of
*CO
*CHxO
on
Cu
restricts
selectivity
toward
CH4.
Alloying
a
secondary
metal
in
provides
new
freedom
break
relationship,
thus
regulating
product
distribution.
This
paper
describes
controllable
electrodeposition
approach
alloying
with
oxophilic
(M)
steer
pathway
The
optimized
La5Cu95
electrocatalyst
exhibits
CH4
Faradaic
efficiency
64.5%,
partial
current
density
193.5
mA
cm-2.
introduction
La
could
lower
barrier
for
hydrogenation
by
strengthening
M-O
bond,
would
also
promote
breakage
C-O
bond
*CH3O
formation
work
avenue
design
Cu-based
electrocatalysts
achieve
CO2RR
through
modulation
behaviors
key
intermediates.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(15), С. 8656 - 8664
Опубликована: Апрель 8, 2023
Copper
(Cu),
a
promising
catalyst
for
electrochemical
CO2
reduction
(CO2R)
to
multi-electron
products,
suffers
from
an
unavoidable
and
uncontrollable
reconstruction
process
during
the
reaction,
which
not
only
may
lead
deactivation
but
also
brings
great
challenges
exploration
of
structure-performance
relationship.
Herein,
we
present
efficient
strategy
stabilizing
Cu
with
silica
synthesize
reconstruction-resistant
CuSiOx
amorphous
nanotube
catalysts
abundant
atomic
Cu-O-Si
interfacial
sites.
The
strong
interaction
between
makes
sites
ultrastable
in
CO2R
reaction
without
any
apparent
reconstruction,
thus
exhibiting
high
CO2-to-CH4
selectivity
(72.5%)
stability
(FECH4
remains
above
60%
after
12
h
test).
A
remarkable
conversion
rate
0.22
μmol
cm-2
s-1
was
achieved
flow
cell
device.
This
work
provides
very
route
design
highly
active
stable
Cu-based
catalysts.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(21)
Опубликована: Март 8, 2022
Developing
robust
electrocatalysts
and
advanced
devices
is
important
for
electrochemical
carbon
dioxide
(CO2
)
reduction
toward
the
generation
of
valuable
chemicals.
We
present
herein
a
carbon-confined
indium
oxide
electrocatalyst
stable
efficient
CO2
reduction.
The
reductive
corrosion
oxidative
to
metallic
state
during
electrolysis
could
be
prevented
by
protection,
applied
layer
also
optimizes
reaction
intermediate
adsorption,
which
enables
both
high
selectivity
activity
In
liquid-phase
flow
cell,
formate
exceeds
90
%
in
wide
potential
window
from
-0.8
V
-1.3
vs.
RHE.
continuous
production
ca.
0.12
M
pure
formic
acid
solution
further
demonstrated
at
current
density
30
mA
cm-2
solid-state
electrolyte
mediated
reactor.
This
work
provides
significant
concepts
parallel
development
carbon-neutral
technologies.
ACS Catalysis,
Год журнала:
2022,
Номер
12(24), С. 15230 - 15240
Опубликована: Ноя. 29, 2022
Electrochemical
reduction
of
CO2
to
obtain
high-value-added
feedstocks
is
a
promising
strategy
alleviate
the
energy
crisis.
Cu-based
catalysts
generate
multi-carbon
products
with
high
activity
in
reaction
(CO2RR),
although
great
challenges
remain
selectivity
and
stability
catalysts.
Here,
highly
active
Cu/Cu2O
nanoclusters
were
produced
via
situ
electrochemical
reconstruction
using
Cu–N
coordinated
MOFs
as
precursors
for
selective
C2H4
synthesis,
showing
Faradaic
efficiency
70.2
±
1.7%
toward
partial
current
density
12.38
mA·cm–2
at
−1.03
V
vs
RHE
CO2RR.
In
infrared
spectroscopy
observation
*CO*CO
*CO*COH
intermediates
confirmed
formation
pathway,
while
Raman
spectroscopy,
ex
XPS,
HRTEM
evidenced
that
coexisting
Cu2O
Cu
sites.
The
method
could
be
used
synthesize
electroreduction.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(11)
Опубликована: Янв. 20, 2023
Electrochemical
CO2
reduction
reaction
(CO2
RR)
to
chemical
fuels
such
as
formate
offers
a
promising
pathway
carbon-neutral
future,
but
its
practical
application
is
largely
inhibited
by
the
lack
of
effective
activation
molecules
and
pH-universal
feasibility.
Here,
we
report
an
electronic
structure
manipulation
strategy
electron-rich
Bi
nanosheets,
where
electrons
transfer
from
Cu
donor
acceptor
in
bimetallic
Cu-Bi,
enabling
RR
towards
with
concurrent
high
activity,
selectivity
stability
(acidic,
neutral
alkaline)
electrolytes.
Combined
situ
Raman
spectra
computational
calculations
unravel
that
promotes
⋅-
formation
activate
molecules,
enhance
adsorption
strength
*OCHO
intermediate
up-shifted
p-band
center,
thus
leading
superior
activity
formate.
Further
integration
robust
nanosheets
into
III-V-based
photovoltaic
solar
cell
results
unassisted
artificial
leaf
solar-to-formate
(STF)
efficiency
13.7
%.