Inorganic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Июнь 1, 2025
Iron
porphyrins
are
extensively
utilized
as
molecular
catalysts
in
the
electrocatalytic
CO2
reduction
reaction
(CO2RR).
While
current
research
primarily
investigates
impact
of
peripheral
substitution
and
second
coordination
sphere
effects,
role
π-system
governing
Fe-porphyrins'
redox
catalytic
properties
CO2RR
has
received
limited
systematic
investigation.
To
that
end,
we
have
prepared
thoroughly
characterized,
both
spectroscopically
electrochemically,
a
series
Fe-porphyrins
with
varying
numbers
π-orbitals
involved
conjugation.
We
observed
correlation
between
thermodynamics
kinetics
number
atomic
orbitals
their
π-system.
Notably,
bicycloporphyrins
lowest
π-system,
[FeCl(TbcTPP)]
[FeCl(TbcP)],
exhibit
lower
rate
constants
TOFmax
values
than
[FeCl(TPP)]
reference
catalyst.
Interestingly,
benzoporphyrins
[FeCl(TBP)]
[FeCl(TBTPP)],
more
display
two
different
cycles,
depending
on
applied
potential.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(43)
Опубликована: Май 24, 2024
Porphyrin
atropisomerism,
which
arises
from
restricted
σ-bond
rotation
between
the
macrocycle
and
a
sufficiently
bulky
substituent,
was
identified
in
1969
by
Gottwald
Ullman
5,10,15,20-tetrakis(o-hydroxyphenyl)porphyrins.
Henceforth,
an
entirely
new
field
has
emerged
utilizing
this
transformative
tool.
This
review
strives
to
explain
consequences
of
atropisomerism
porphyrins,
methods
have
been
developed
for
their
separation
analysis
present
diverse
array
applications.
Porphyrins
alone
possess
intriguing
properties
structure
can
be
easily
decorated
molded
specific
function.
Therefore,
serves
as
tool,
making
it
possible
obtain
even
molecular
shape.
Atropisomerism
thoroughly
exploited
catalysis
recognition
yet
presents
both
challenges
opportunities
medicinal
chemistry.
In
this
series
of
articles,
the
Board
Members
ChemSusChem
review
recent
research
articles
that
they
consider
exceptional
quality
and
importance
for
sustainability.
This
entry
features
Prof.
Rui
Cao,
who
discusses
how
tuning
second-sphere
environments
Fe
porphyrins
can
improve
activity
selectivity
CO2
reduction.
Substituents
with
proton
relay
capability,
hydrogen-bonding,
electrostatic
have
significant
impact
on
efficiency
electrocatalytic
reduction
reaction.
Abstract
Mechanistic
studies
involving
characterization
of
crucial
intermediates
are
desirable
for
rational
optimization
molecular
catalysts
toward
CO
2
reduction,
while
fundamental
challenges
associated
with
such
studies.
Herein
we
present
the
systematic
mechanistic
investigations
on
a
pyrene‐appended
Co
II
macrocyclic
catalyst
in
comparison
its
pyrene‐free
prototype.
The
comparative
results
also
verify
reasons
higher
catalytic
activity
pyrene‐tethered
noble‐metal‐free
photoreduction
various
photosensitizers,
where
remarkable
apparent
quantum
yield
36±3
%
at
425
nm
can
be
obtained
selective
production.
Electrochemical
and
spectroelectrochemical
conjunction
DFT
calculations
between
two
have
characterized
key
CO‐bound
revealed
their
different
CO‐binding
behavior,
demonstrating
that
pyrene
group
endows
corresponding
lower
potential,
stability,
greater
ease
release,
all
which
contribute
to
better
performance.
Abstract
The
conversion
of
CO
2
into
fuels
or
commodity
chemicals
by
electrochemical
photochemical
reduction
is
a
promising
strategy
to
relieve
the
ongoing
energy
crisis
and
increasing
environmental
pollution.
Inspired
naturally
occurring
bimetalloenzymes,
we
have
designed
hetero–bimetallic
catalysts
(
FeM
)
that
involve
linking
an
iron
tetraphenylporphyrin
FeP
with
tripyridylamine
(TPA)
moiety,
which
provides
distal
chelating
site
for
Cu
2+
Zn
.
We
found
introduction
greatly
enhances
its
efficiency
as
catalyst
To
gain
insights
observed
synergistic
effect,
performed
mechanistic
studies
together
density
functional
theory
(DFT)
calculations.
Our
results
show
activates
towards
due
Lewis
acidity;
it
also
functions
oxo
acceptor
from
efficient
visible‐light‐driven
using
either
[Ru(bpy)
3
]
Cl
fac
‐Ir(ppy)
(where
bpy=2,2’‐bipyridine,
ppy=2‐phenylpyridine)
photosensitizer
1,3‐dimethyl‐2‐phenyl‐2,3‐dihydro‐1H‐benzo[d]
imidazole
(BIH)
sacrificial
reductant.
Again,
catalytic
enhanced
presence
provide
general
design
series
hetero‐bimetallic
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 31, 2024
Abstract
Porous
organic
polymers
have
shown
great
potential
in
photocatalytic
CO
2
reduction
due
to
their
unique
tunable
structure
favoring
gas
adsorption
and
metal
sites
integration.
However,
efficient
photocatalysis
porous
is
greatly
limited
by
the
low
surface
reactivity
electron
mobility
of
bulk
structure.
Herein,
we
incorporate
TiO
nanoparticles
Ni(II)
into
a
layered
cationic
imidazolium
polymer
(IP),
which
moieties
free
anions
can
stabilize
key
intermediates
enhance
reaction
kinetics
reduction.
During
reaction,
/NiIP
situ
exfoliated
nanosheets
(NSs)
with
more
accessible
active
shorten
transport
pathways.
The
formed
/NiIP‐NSs
exhibit
an
impressively
high
production
rate
as
54.9
mmol
⋅
g
−1
h
selectivity
99.9
%.
embedding
could
improve
efficiency
so
facilitate
photochemical
stripping
process
polymer.
Moreover,
assistance
possess
excellent
stability
during
recycling
experiments
comparison
rapidly
declined
activity
NiIP‐NSs.
This
work
presents
new
strategy
construct
highly
photocatalysts
for
Accounts of Chemical Research,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 27, 2025
ConspectusIn
the
search
for
efficient
and
selective
electrocatalysts
capable
of
converting
greenhouse
gases
to
value-added
products,
enzymes
found
in
naturally
existing
bacteria
provide
basis
most
approaches
toward
electrocatalyst
design.
Ni,Fe-carbon
monoxide
dehydrogenase
(Ni,Fe-CODH)
is
one
such
enzyme,
with
a
nickel-iron-sulfur
cluster
named
C-cluster,
where
CO2
binds
converted
CO
at
high
rates
near
thermodynamic
potential.
In
this
Account,
we
divide
enzyme's
catalytic
contributions
into
three
categories
based
on
location
function.
We
also
discuss
how
computational
techniques
crucial
insight
implementing
these
findings
homogeneous
reduction
electrocatalysis
design
principles.
The
binding
sites
(e.g.,
Ni
"unique"
Fe
ion)
along
ligands
that
support
it
iron-sulfur
cluster)
form
primary
coordination
sphere.
This
replicated
molecular
via
metal
center
ligand
framework
substrate
binds.
sphere
has
direct
impact
electronic
configuration
catalyst.
By
computationally
modeling
series
Co
complexes
bipyridyl-N-heterocyclic
carbene
frameworks
varying
degrees
planarity,
were
able
closely
examine
controls
product
distribution
between
H2
catalysts.
secondary
(SCS)
Ni,Fe-CODH
contains
residues
proximal
active
site
pocket
hydrogen-bonding
stabilizations
necessary
reaction
proceed.
Enhancing
SCS
when
synthesizing
new
catalysts
involves
substituting
functional
groups
onto
interaction
substrate.
To
analyze
endless
possible
substitutions,
are
ideal
deciphering
intricacies
substituent
effects,
as
demonstrated
an
array
imidazolium-functionalized
Mn
Re
bipyridyl
tricarbonyl
complexes.
examining
electrostatic
interactions
ligand,
substrate,
proton
source
lowered
activation
energy
barriers,
determined
best
pinpoint
additions.
outer
comprises
remaining
parts
Ni,Fe-CODH,
elaborate
protein
matrix,
solvent
interactions,
remote
metalloclusters.
challenge
elucidating
replicating
role
vast
matrix
understandably
led
localized
focus
spheres.
However,
certain
portions
Ni,Fe-CODH's
expansive
scaffold
suggested
be
catalytically
relevant
despite
considerable
distance
from
site.
Closer
studies
relatively
overlooked
areas
nature's
exceptionally
proficient
may
continually
improve
upon
protocols.
Mechanistic
analysis
cobalt
phthalocyanines
(CoPc)
immobilized
carbon
nanotubes
(CoPc/CNT)
reveals
microenvironment
effects
unlock
CoPc
molecule's
previously
inaccessible
intrinsic
ability
convert
MeOH.
Our
research
suggests
incorporating
spheres
holistic
approach
vital
advancing
viability
mitigating
climate
disruption.
Computational
methods
allow
us
transition
states
determine
minimize
key
barriers.
