Angewandte Chemie International Edition,
Journal Year:
2018,
Volume and Issue:
57(24), P. 7071 - 7075
Published: April 23, 2018
Hydrothermally
stable,
acid-resistant
nickel
catalysts
are
highly
desired
in
hydrogenation
reactions,
but
such
a
catalyst
remains
absent
owing
to
the
inherent
vulnerability
of
under
acidic
conditions.
An
ultra-durable
Ni-N-C
single-atom
(SAC)
has
now
been
developed
that
possesses
remarkable
Ni
content
(7.5
wt
%)
required
for
practical
usage.
This
SAC
shows
not
only
high
activities
various
unsaturated
substrates
also
unprecedented
durability
one-pot
conversion
cellulose
very
harsh
conditions
(245
°C,
60
bar
H2
,
presence
tungstic
acid
hot
water).
Using
integrated
spectroscopy
characterization
and
computational
modeling,
active
site
structure
is
identified
as
(Ni-N4)⋅⋅⋅N,
where
significantly
distorted
octahedral
coordination
pyridinic
N
constitute
frustrated
Lewis
pair
heterolytic
dissociation
dihydrogen,
robust
covalent
chemical
bonding
between
atoms
accounts
its
ultrastability.
ACS Catalysis,
Journal Year:
2018,
Volume and Issue:
9(1), P. 130 - 146
Published: Nov. 28, 2018
Heterogeneous
catalysts
based
on
metal–organic
frameworks
(MOFs)
have
attracted
significant
attention
in
the
past
two
decades.
The
well-defined
structure
of
these
molecular
materials
enables
rational
design
catalytic
centers.
While
early
efforts
MOF
catalysis
mainly
focused
synthesis
fine
chemicals,
MOFs
recently
been
explored
for
solid–gas
phase
to
produce
commodity
chemicals.
In
this
Perspective,
we
summarize
several
opportunities
using
and
discuss
limitations
reactions.
We
illustrate
use
fundamental
mechanistic
studies
industrially
relevant
catalysts.
attempt
identify
specific
reactions
that
can
benefit
from
also
point
out
scenarios
where
is
unlikely
replace
current
technology.
hope
our
in-depth
discussion
critical
assessment
will
promote
development
new
MOF-based
heterogeneous
Chemical Reviews,
Journal Year:
2020,
Volume and Issue:
120(16), P. 8641 - 8715
Published: July 16, 2020
Owing
to
their
molecular
building
blocks,
yet
highly
crystalline
nature,
metal-organic
frameworks
(MOFs)
sit
at
the
interface
between
molecule
and
material.
Their
diverse
structures
compositions
enable
them
be
useful
materials
as
catalysts
in
heterogeneous
reactions,
electrical
conductors
energy
storage
transfer
applications,
chromophores
photoenabled
chemical
transformations,
beyond.
In
all
cases,
density
functional
theory
(DFT)
higher-level
methods
for
electronic
structure
determination
provide
valuable
quantitative
information
about
properties
that
underpin
functions
of
these
frameworks.
However,
there
are
only
two
general
modeling
approaches
conventional
software
packages:
those
treat
extended,
periodic
solids,
discrete
molecules.
Each
approach
has
features
benefits;
both
have
been
widely
employed
understand
emergent
chemistry
arises
from
formation
interface.
This
Review
canvases
date,
with
emphasis
placed
on
application
explore
reactivity
electron
using
periodic,
molecular,
embedded
models.
includes
(i)
computational
considerations
such
how
functional,
k-grid,
other
model
variables
selected
insights
into
MOF
properties,
(ii)
extended
solid
models
MOFs
rather
than
molecules,
(iii)
mechanics
cluster
extraction
subsequent
enabled
by
models,
(iv)
catalytic
studies
solids
clusters
thereof,
(v)
embedded,
mixed-method
approaches,
which
simulate
a
fraction
material
one
level
remainder
another
dissimilar
theoretical
implementation.
Chemical Reviews,
Journal Year:
2018,
Volume and Issue:
118(22), P. 10840 - 11022
Published: Oct. 29, 2018
Heme-copper
oxidases
(HCOs)
are
terminal
enzymes
on
the
mitochondrial
or
bacterial
respiratory
electron
transport
chain,
which
utilize
a
unique
heterobinuclear
active
site
to
catalyze
4H+/4e–
reduction
of
dioxygen
water.
This
process
involves
proton-coupled
transfer
(PCET)
from
tyrosine
(phenolic)
residue
and
additional
redox
events
coupled
transmembrane
proton
pumping
ATP
synthesis.
Given
that
HCOs
large,
complex,
membrane-bound
enzymes,
bioinspired
synthetic
model
chemistry
is
promising
approach
better
understand
heme–Cu-mediated
reduction,
including
details
movements.
review
encompasses
important
aspects
heme–O2
copper–O2
(bio)chemistries
as
they
relate
design
interpretation
small
molecule
systems
provides
perspectives
fundamental
coordination
chemistry,
can
be
applied
understanding
HCO
activity.
We
focus
recent
advancements
studies
heme–Cu
models,
evaluating
experimental
computational
results,
highlight
structure–function
relationships.
Finally,
we
provide
an
outlook
for
future
potential
contributions
inorganic
discuss
their
implications
with
relevance
biological
O2-reduction.
Nature Communications,
Journal Year:
2021,
Volume and Issue:
12(1)
Published: Feb. 22, 2021
Abstract
As
a
100%
atom-economy
process,
direct
oxidation
of
methane
into
methanol
remains
as
grand
challenge
due
to
the
dilemma
between
activation
and
over-oxidation
methanol.
Here,
we
report
that
water
enabled
mild
with
>99%
selectivity
over
Au
single
atoms
on
black
phosphorus
(Au
1
/BP)
nanosheets
under
light
irradiation.
The
mass
activity
/BP
reached
113.5
μmol
g
catal
−1
in
pressured
33
bar
mixed
gas
(CH
4
:O
2
=
10:1)
at
90
°C
irradiation
(1.2
W),
while
energy
was
43.4
kJ
mol
.
Mechanistic
studies
revealed
assisted
O
generate
reactive
hydroxyl
groups
•OH
radicals
Hydroxyl
reacted
form
CH
3
*
species,
followed
by
via
Considering
recycling
during
whole
can
also
regard
catalyst.
