Inorganic Chemistry,
Год журнала:
2024,
Номер
63(17), С. 7571 - 7588
Опубликована: Апрель 18, 2024
Recently,
global-scale
efforts
have
been
conducted
for
the
electroreduction
of
CO2
as
a
potentially
beneficial
pathway
conversion
greenhouse
gases
to
useful
chemicals
and
renewable
fuels.
This
study
focuses
on
development
selective
sustainable
electrocatalysts
reduction
aqueous
CO.
A
RuIIcomplex
[Ru(tptz)(ACN)Cl2]
(RCMP)
(tptz
=
2,4,6-tris(2-pyridyl)-1,3,5-triazine,
ACN
acetonitrile)
was
prepared
molecular
electrocatalyst
reaction
in
an
solution.
Density
functional
theory-calculated
frontier
orbitals
suggested
that
tptz
ligand
plays
key
role
dictating
electrocatalytic
reactions.
The
RCMP
grafted
onto
graphene
oxide
(GO)
surface
both
noncovalently
(GO/RCMP)
covalently
(GO-RCMP).
field
emission
scanning
electron
microscopy
elemental
distribution
analyses
revealed
homogeneous
complex
GO
sheet.
photoluminescence
spectra
confirmed
accelerated
charge-transfer
nanohybrids.
Compared
bare
complex,
GO-RCMP
GO/RCMP
nanohybrids
showed
enhanced
activity,
achieving
>95%
90%
Faradaic
efficiencies
CO
production
at
more
positive
onset
potentials,
respectively.
nanohybrid
demonstrated
outstanding
activity
with
current
∼84
μA.
offers
perspective
outer-
inner-sphere
electron-transfer
mechanisms
electrochemical
energy
systems.
ACS Nano,
Год журнала:
2024,
Номер
18(14), С. 9823 - 9851
Опубликована: Март 28, 2024
With
the
increasingly
serious
greenhouse
effect,
electrochemical
carbon
dioxide
reduction
reaction
(CO2RR)
has
garnered
widespread
attention
as
it
is
capable
of
leveraging
renewable
energy
to
convert
CO2
into
value-added
chemicals
and
fuels.
However,
performance
CO2RR
can
hardly
meet
expectations
because
diverse
intermediates
complicated
processes,
necessitating
exploitation
highly
efficient
catalysts.
In
recent
years,
with
advanced
characterization
technologies
theoretical
simulations,
exploration
catalytic
mechanisms
gradually
deepened
electronic
structure
catalysts
their
interactions
intermediates,
which
serve
a
bridge
facilitate
deeper
comprehension
structure-performance
relationships.
Transition
metal-based
(TMCs),
extensively
applied
in
CO2RR,
demonstrate
substantial
potential
for
further
modulation,
given
abundance
d
electrons.
Herein,
we
discuss
representative
feasible
strategies
modulate
catalysts,
including
doping,
vacancy,
alloying,
heterostructure,
strain,
phase
engineering.
These
approaches
profoundly
alter
inherent
properties
TMCs
interaction
thereby
greatly
affecting
rate
pathway
CO2RR.
It
believed
that
rational
design
modulation
fundamentally
provide
viable
directions
development
toward
conversion
many
other
small
molecules.
ACS Nano,
Год журнала:
2024,
Номер
18(9), С. 7192 - 7203
Опубликована: Фев. 22, 2024
Electrocatalytic
carbon
dioxide
reduction
reaction
(CO2RR)
toward
value-added
chemicals/fuels
has
offered
a
sustainable
strategy
to
achieve
carbon-neutral
energy
cycle.
However,
it
remains
great
challenge
controllably
and
precisely
regulate
the
coordination
environment
of
active
sites
in
catalysts
for
efficient
generation
targeted
products,
especially
multicarbon
(C2+)
products.
Herein
we
report
engineering
metal
centers
polymers
electroreduction
CO2
C2+
products
under
neutral
conditions.
Significantly,
Cu
polymer
with
Cu–N2S2
configuration
(Cu–N–S)
demonstrates
superior
Faradaic
efficiencies
61.2%
82.2%
ethylene
respectively,
compared
selective
formic
acid
on
an
analogous
Cu–I2S2
mode
(Cu–I–S).
In
situ
studies
reveal
balanced
formation
atop
bridge
*CO
intermediates
Cu–N–S,
promoting
C–C
coupling
production.
Theoretical
calculations
suggest
that
can
induce
electronic
modulations
sites,
where
d-band
center
is
upshifted
Cu–N–S
stronger
selectivity
Consequently,
displays
trend
while
Cu–I–S
favors
due
suppression
couplings
pathways
large
barriers.
Green Chemistry,
Год журнала:
2024,
Номер
26(10), С. 6209 - 6218
Опубликована: Янв. 1, 2024
A
green,
efficient
high-gravity-assisted
approach
was
proposed
to
synthesize
MOF-74–Co
with
controllable
particle
size,
high
crystallinity,
large
specific
surface
area
and
excellent
CO
2
adsorption
performance.
ACS Materials Letters,
Год журнала:
2023,
Номер
5(12), С. 3212 - 3221
Опубликована: Ноя. 6, 2023
The
electrochemical
carbon
dioxide
(CO2)
reduction
reaction
(CO2RR)
has
been
considered
as
a
promising
approach
to
convert
atmospheric
CO2
value-added
chemicals
promote
neutrality.
However,
developing
electrocatalysts
with
superior
activity
and
high
selectivity
toward
individual
products
remains
great
challenge.
Herein
we
report
the
electronic
structure
modulation
of
unconventional
phase
metal
nanomaterials
achieve
highly
efficient
electroreduction.
It
found
that
growing
cerium
oxide
(CeOx)
nanostructures
on
4H/face-centered
cubic
(fcc)
gold
(Au)
nanorods
can
significantly
enhance
their
catalytic
conversion
monoxide.
X-ray
analysis
indicates
change
4H/fcc
Au
after
CeOx
overgrowth.
In-situ
attenuated
total
reflection
infrared
spectroscopy
measurements
reveal
HCO3–
concentration
near
surface
Au-CeOx
heteronanostructures
is
much
higher
than
nanorods,
facilitating
process.
Density
functional
theory
calculations
suggest
activation
effect
nanorod
for
electrocatalytic
CO2RR.
synergy
between
promotes
formation
carboxyl
(*COOH)
species
thus
boosts
CO2RR
performance.
This
work
highlights
importance
rational
regulation
unusual
small
molecules.
