Angewandte Chemie,
Год журнала:
2023,
Номер
135(23)
Опубликована: Март 27, 2023
Abstract
We
report
a
ternary
hybrid
photocatalyst
architecture
with
tailored
interfaces
that
boost
the
utilization
of
solar
energy
for
photochemical
CO
2
reduction
by
synergizing
electron
and
heat
flows
in
photocatalyst.
The
comprises
cobalt
phthalocyanine
(CoPc)
molecules
assembled
on
multiwalled
carbon
nanotubes
(CNTs)
are
decorated
nearly
monodispersed
cadmium
sulfide
quantum
dots
(CdS
QDs).
CdS
QDs
absorb
visible
light
generate
electron‐hole
pairs.
CNTs
rapidly
transfer
photogenerated
electrons
from
to
CoPc.
CoPc
then
selectively
reduce
CO.
interfacial
dynamics
catalytic
behavior
clearly
revealed
time‐resolved
situ
vibrational
spectroscopies.
In
addition
serving
as
highways,
black
body
property
CNT
component
can
create
local
photothermal
heating
activate
amine‐captured
,
namely
carbamates,
direct
conversion
without
additional
input.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(23)
Опубликована: Март 27, 2023
We
report
a
ternary
hybrid
photocatalyst
architecture
with
tailored
interfaces
that
boost
the
utilization
of
solar
energy
for
photochemical
CO2
reduction
by
synergizing
electron
and
heat
flows
in
photocatalyst.
The
comprises
cobalt
phthalocyanine
(CoPc)
molecules
assembled
on
multiwalled
carbon
nanotubes
(CNTs)
are
decorated
nearly
monodispersed
cadmium
sulfide
quantum
dots
(CdS
QDs).
CdS
QDs
absorb
visible
light
generate
electron-hole
pairs.
CNTs
rapidly
transfer
photogenerated
electrons
from
to
CoPc.
CoPc
then
selectively
reduce
CO.
interfacial
dynamics
catalytic
behavior
clearly
revealed
time-resolved
situ
vibrational
spectroscopies.
In
addition
serving
as
highways,
black
body
property
CNT
component
can
create
local
photothermal
heating
activate
amine-captured
,
namely
carbamates,
direct
conversion
without
additional
input.
ACS Sustainable Chemistry & Engineering,
Год журнала:
2024,
Номер
12(16), С. 6093 - 6101
Опубликована: Март 12, 2024
The
electrocatalytic
CO2
reduction
reaction
(CO2RR)
to
produce
multicarbon
(C2+)
products
such
as
ethylene
(C2H4)
is
a
promising
method
achieve
carbon
neutrality,
but
it
very
difficult
due
the
high
activation
barrier
of
and
low
selectivity
CO2RR
especially
for
C2+
products.
Herein,
copper
single
atoms
(Cu-SAs)
were
confined
into
nanospace
an
iridium
porphyrin-based
metal–organic
framework
(Ir-PCN-222)
form
(MOF)
composite
(Cu-SAs@Ir-PCN-222-PA)
with
dual
active
sites
Ir-porphyrin
Cu-SAs
through
precoordination
confinement
strategy.
Catalytic
results
disclosed
that
Cu-SAs@Ir-PCN-222-PA
could
drive
C2H4
faradaic
efficiency
(FE)
(70.9%)
current
density
20.4
mA·cm–2.
When
H-cell
was
replaced
by
flow
cell,
be
increased
161
mA·cm–2
still
FE
(66.9%).
Mechanism
studies
suggested
in
Cu-SAs@Ir-PCN-222-PA-catalyzed
electroreduction
reaction,
CO
first
generated
on
then
moved
adsorbed
*CO
intermediate
nearby
Cu-SAs,
after
that,
C–C
coupling
process
carried
out
provide
product
C2H4.
This
work
offers
new
kind
MOF
electrocatalysts
generate
Green Chemistry,
Год журнала:
2024,
Номер
26(18), С. 9503 - 9528
Опубликована: Янв. 1, 2024
An
overview
of
sustainability
outcomes
provided
by
flow
chemistry
is
reviewed
for
a
comprehensive
understanding
and
holistic
perspective.
Future
trends
potential
innovations
are
also
forecast.
ACS Organic & Inorganic Au,
Год журнала:
2023,
Номер
3(6), С. 384 - 392
Опубликована: Авг. 22, 2023
The
selective
reduction
of
carbon
dioxide
remains
a
significant
challenge
due
to
the
complex
multielectron/proton
transfer
process,
which
results
in
high
kinetic
barrier
and
production
diverse
products.
Inspired
by
electrostatic
H-bonding
interactions
observed
second
sphere
[NiFe]-CODH
enzyme,
researchers
have
extensively
explored
these
regulate
proton
transfer,
stabilize
intermediates,
ultimately
improve
performance
catalytic
CO2
reduction.
In
this
work,
series
cobalt(II)
tetraphenylporphyrins
with
varying
numbers
redox-active
nitro
groups
were
synthesized
evaluated
as
electrocatalysts.
Analyses
redox
properties
complexes
revealed
consistent
relationship
between
number
corresponding
accepted
electron
ligand
at
−1.59
V
vs.
Fc+/0.
Among
catalysts
tested,
TNPPCo
four
exhibited
most
efficient
activity
turnover
frequency
4.9
×
104
s–1
onset
potential
820
mV
more
positive
than
that
parent
TPPCo.
Furthermore,
frequencies
increased
higher
groups.
These
demonstrate
promising
design
strategy
incorporating
multielectron
ligands
into
enhance
performance.
Advanced Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 22, 2025
To
efficiently
capture,
activate,
and
transform
small
molecules,
metalloenzymes
have
evolved
to
integrate
a
well-organized
pocket
around
the
active
metal
center.
Within
this
cavity,
second
coordination
sphere
functionalities
are
precisely
positioned
optimize
rate,
selectivity,
energy
cost
of
catalytic
reactions.
Inspired
by
strategy,
an
artificial
distal
defined
preorganized
3D
strap
is
introduced
on
iron-porphyrin
catalyst
(sc-Fe)
for
CO2-to-CO
electrocatalytic
reduction.
Combined
electrochemical,
kinetic,
computational
studies
demonstrate
that
adequate
positioning
carboxylate/carboxylic
group
acting
in
synergy
with
trapped
water
molecule
within
remarkably
enhances
reaction
turnover
frequency
(TOF)
four
orders
magnitude
compared
perfluorinated
iron-tetraphenylporphyrin
(F20Fe)
operating
at
similar
low
overpotential.
A
proton-coupled
electron
transfer
(PCET)
found
be
key
process
responsible
unexpected
protonation
coordinating
carboxylate,
which,
upon
CO2
insertion,
shifts
from
first
play
possible
secondary
role
as
proton
relay.
