It
remains
challenging
for
the
fabrication
of
metal-organic
framework
(MOF)/semiconductor
heterojunction
photocatalysts
with
close
contact
interfaces.
In
this
work,
a
novel
MOF/semiconductor
photocatalyst
consisting
H2O2-modified
TiO2
nanotubes
(H2O2-TNTs)
and
MIL-88B(Fe)-NH2
(labeled
as
H-T/M)
was
firstly
constructed
based
on
hydrogen-bonded
combination
between
O
atoms
from
–OOH
groups
resulting
H2O2
absorbed
surface
H
–NH2
group
in
MOF.
The
significantly
enhanced
photocatalytic
property
H-T/M
reducing
Cr(VI)
under
visible
light
irradiation
could
be
ascribed
to
accelerated
interfacial
electron
transfer
dynamics
by
channel
hydrogen
bonds
(N···H–O–O–Ti),
which
extracted
femtosecond
transient
absorption
spectroscopy
(fs-TAS).
Moreover,
built-in
electric
field
differences
charge
density
functional
theory
(DFT)
calculations
provide
driving
force
transfer.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(49)
Published: Aug. 13, 2024
Abstract
The
photoconversion
of
CO
2
into
valuable
chemical
products
using
solar
energy
is
a
promising
strategy
to
address
both
and
environmental
challenges.
However,
the
strongly
adsorbed
frequently
impedes
seamless
advancement
subsequent
reaction
by
significantly
increasing
activation
energy.
Here,
we
present
BiFeO
3
material
with
lattice
strain
that
collaboratively
regulates
d/p‐2π*
orbitals
hybridization
between
metal
sites
*CO
as
well
*COOH
intermediates
achieve
rapid
conversion
solidly
critical
intermediates,
accelerating
overall
reduction
kinetics.
Quasi
in
situ
X‐ray
photoelectron
spectroscopy
Fourier
Transform
infrared
combined
theoretical
calculation
reveals
optimized
Fe
enhance
adsorption
effect
,
continuous
internal
electrons
are
rapidly
transferred
injected
surface
under
condition
illumination,
which
promotes
formation
stability
*COOH.
Certainly,
performance
photoreduction
improved
12.81‐fold
compared
base
material.
This
work
offers
new
perspective
for
process
.
Langmuir,
Journal Year:
2024,
Volume and Issue:
40(17), P. 9233 - 9243
Published: April 16, 2024
Ethyl
methyl
carbonate
(EMC)
is
a
crucial
solvent
extensively
utilized
in
lithium-ion
battery
electrolytes;
the
transesterification
of
dimethyl
(DMC)
with
ethanol
pivotal
reaction
for
EMC
production.
However,
this
faces
challenges
due
to
trade-off
between
catalytic
activity
and
selectivity
from
basic
catalysts.
In
issue,
we
report
an
innovative
strategy
through
fine-tuning
electron-donor
capability
phenolate
anion
([PhO])
novel
poly(ionic
liquid)
(PIL)
framework,
as
synthesized
via
alkylation
1,3,5-tris(bromomethyl)benzene,
biphenyldiimidazole,
N,N′-carbonyldiimidazole
(CDI)
trigger
targeted
basicity
that
can
directionally
catalyze
DMC
ethanol,
so
achieve
both
ultrahigh
toward
EMC.
By
varying
substituent
groups
electron-withdrawing
electron-donating
effects
on
anion,
PILs
show
expected
changes
performance,
following
well
trend
charge
density
these
substituted
anions.
The
optimized
catalyst
[CPIL-CDI][MeOPhO],
induced
by
p-methoxyphenolate
anions,
allows
extraordinary
yield
72.19%
91.48%
under
mild
conditions
without
any
process
intensifications,
suppressing
all
reported
catalysts
date.
Outcomes
approaches
shown
work
have
potential
expedite
systematic
design
cations
anions
within
industrial-scale
production
environmentally
friendly
processes.
