Heterogeneity
engineering
provides
an
effective
route
to
manipulate
the
chemical
and
physical
properties
of
covalent
organic
frameworks
(COFs)
but
is
still
under
development
for
their
single-crystal
form.
Here,
we
report
strategy
based
on
a
combination
template-assisted
modulated
synthesis
with
one-pot
crystallization-reduction
method
directly
construct
ordered
macro-microporous
single
crystals
amine-linked
three-dimensional
(3D)
COF
(OM-COF-300-SR).
In
this
strategy,
colloidal
crystal-templating
not
only
assists
formation
macropores
also
greatly
facilitates
in
situ
conversion
linkages
(from
imine
amine)
COF-300
crystals.
The
as-synthesized
OM-COF-300-SR120
exhibits
reversible
symmetry
change
from
tetragonal
I41/a
monoclinic
I2/c
space
group
after
activation,
which
was
observed
previously.
On
other
hand,
allows
flexible
control
over
degree
amination
0
100%,
as
determined
by
X-ray
photoelectron
spectroscopy
(XPS)
analysis)
regulate
band
gap
2.57
2.81
eV)
optimization
photocatalytic
activity.
high
embedded
render
superior
activity
(with
reaction
rate
constant
0.9572
min-1)
its
nonmacroporous
counterpart
(NM-COF-300-SR120,
0.2303
degradation
rhodamine
B.
addition,
significant
contribution
confront
mass
transfer
resistance
confirmed
much
higher
catalytic
Au/OM-COF-300-SR120
parameter
7.96
×
103
s-1
mol-1)
compared
Au/NM-COF-300-SR120
(1.43
model
reduction
4-nitrophenol
NaBH4.
