Nature Communications,
Год журнала:
2021,
Номер
12(1)
Опубликована: Фев. 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.
ACS Catalysis,
Год журнала:
2020,
Номер
10(9), С. 4906 - 4913
Опубликована: Апрель 1, 2020
Selective
oxidation
to
produce
target
chemicals
usually
need
activation
of
O2
at
high
temperature
and/or
pressure,
which
have
largely
restricted
its
practical
operation
and
application.
Here,
we
put
forward
a
radical
relay
strategy
coupling
photoelectrochemical
(PEC)
water
toward
efficiently
selective
conversion
benzyl
alcohol
(BA)
benzaldehyde
(BAD).
An
illuminated
BiVO4
(BVO)
photoanode
covered
with
an
ultrathin
(∼3
nm)
hydrothermally
synthesized
layered
double
hydroxide
(U-LDH)
catalyst
graphene
(G)
exhibited
>99%
selectivity
BAD
(1.2
V
vs.
RHE).
Mechanistic
studies
DFT
calculation
verified
that
the
hydroxyl
radicals
(·OH)
generated
from
are
bound
surface
U-LDH
through
hydrogen-bonding
interactions
energy
is
lowered.
Fourier
transform
infrared
spectroscopy
showed
BA
adsorbed
catalyst,
but
not.
Thus,
favored
not
only
by
controlled
capacity
·OH
desorption
desired
product
before
further
occurs.
This
work
introduces
alternative
PEC
way
achieve
mild
derivatives
based
on
ternary
G@U-LDH@BVO
catalysts.
Nature Communications,
Год журнала:
2022,
Номер
13(1)
Опубликована: Май 25, 2022
Methane
(CH4)
oxidation
to
high
value
chemicals
under
mild
conditions
through
photocatalysis
is
a
sustainable
and
appealing
pathway,
nevertheless
confronting
the
critical
issues
regarding
both
conversion
selectivity.
Herein,
visible
irradiation
(420
nm),
synergy
of
palladium
(Pd)
atom
cocatalyst
oxygen
vacancies
(OVs)
on
In2O3
nanorods
enables
superior
photocatalytic
CH4
activation
by
O2.
The
optimized
catalyst
reaches
ca.
100
μmol
h-1
C1
oxygenates,
with
selectivity
primary
products
(CH3OH
CH3OOH)
up
82.5%.
Mechanism
investigation
elucidates
that
such
induced
dedicated
function
Pd
single
atoms
boosting
hole
electron
transfer,
respectively.
O2
proven
be
only
source
for
CH3OH
production,
while
H2O
acts
as
promoter
efficient
·OH
production
facilitates
product
desorption
indicated
DFT
modeling.
This
work
thus
provides
new
understandings
simultaneous
regulation
activity
cocatalysts
vacancies.
Nature Communications,
Год журнала:
2021,
Номер
12(1)
Опубликована: Фев. 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.
