In
this
work,
we
constructed
a
novel
heat-resistant
energetic
material
with
four
ring
long
chain
structure
bridged
by
azo
bis
(1,2,4-triazole)
using
electrochemical
synthesis
method.
terms
of
structure,
the
synthesized
1,2-bis(5-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-3-yl)-diazene
(H4AzTT)
exhibits
zwitterionic
properties
and
can
be
obtained
in
form
rare
tetravalent
when
used
as
nitrogen
rich
anion.
Due
to
high
content
molecule
large
conjugated
system
formed
bonds,
H4AzTT
its
salts
(M-AzTT)
exhibit
excellent
thermal
stability
energy
performance.
Among
them,
K4-AzTT·3H2O
possess
highest
decomposition
428
℃.
Specifically,
traditional
chemical
chains
may
result
breakage
or
by-product
generation,
while
method
is
efficient
controllable,
allows
for
direct
salt
(potassium,
lithium,
sodium,
guanidine)
simply
changing
electrolyte.
Electrochemical
testing
situ
ATR-SEIRAS
analysis
showed
that
electro
M-AzTT
occurred
earlier
than
OER.
Therefore,
under
alkaline
conditions,
65%
yield
81.5%
Faraday
efficiency
were
achieved
at
1.7
V
vs.
RHE.
summary,
study
not
only
constructs
super
compounds,
but
also
represents
new
breakthrough
electrochemistry
field
materials.
ACS Applied Materials & Interfaces,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 24, 2024
Carbonyl
azides
are
important
precursors
to
isocyanates
and
used
as
energetic
compounds.
However,
the
further
development
of
these
compounds
is
limited
by
their
inherently
poor
stability.
In
this
study,
we
present
a
new
family
carbonyl
azides,
5-nitro-1H-1,2,4-triazol-3-yl-carbamoyl-azide
(NTCA),
which
was
synthesized
through
in
situ
oxidation
cleavage
amino-tetrazole.
Compared
with
its
precursor
(nitrocarbamoyl
azide,
HNCA),
X-ray
data
quantum
calculations
indicate
that
NTCA
has
much
stronger
conjugation
(dihedral
angle
decreased
from
13.39°
1.35°)
more
H-bonds
(increase
2
7
pairs).
As
result,
exhibits
highest
thermal
stability
(decomposition
temperature
212
°C)
density
(1.820
g
cm
Two
series
of
nitro-substituted
fused
triazole
were
prepared.
All
compounds
have
been
fully
characterized
by
IR,
elemental
analysis,
1H
and
13C
NMR
DSC.
Neutral
a1
b1
exhibit
quite
different
thermostabilities
this
trend
has
extended
to
their
energetic
salts,
which
could
be
explained
the
NBO
analysis
hydrogen
bonds
based
on
single-crystal
parameters.
The
structures
salts
a2,
a3
b3
also
confirmed
X-ray
diffraction.
NCI
Hirshfeld
surfaces
performed
further
understand
relationship
between
properties
regioisomeric
structures.
new
show
good
densities
varying
within
1.66-1.83
g
cm-3,
detonation
velocities
7688-8461
m
s-1
pressures
22.1-26.7
Gpa,
are
insensitive
friction
impact.
High
thermal
stability
(Td
=
274
°C)
combined
with
velocity
(vD
8238
s-1)
highlight
promising
application
for
salt
b2
as
a
high-energy
compound.
In
this
work,
we
constructed
a
novel
heat-resistant
energetic
material
with
four
ring
long
chain
structure
bridged
by
azo
bis
(1,2,4-triazole)
using
electrochemical
synthesis
method.
terms
of
structure,
the
synthesized
1,2-bis(5-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-3-yl)-diazene
(H4AzTT)
exhibits
zwitterionic
properties
and
can
be
obtained
in
form
rare
tetravalent
when
used
as
nitrogen
rich
anion.
Due
to
high
content
molecule
large
conjugated
system
formed
bonds,
H4AzTT
its
salts
(M-AzTT)
exhibit
excellent
thermal
stability
energy
performance.
Among
them,
K4-AzTT·3H2O
possess
highest
decomposition
428
℃.
Specifically,
traditional
chemical
chains
may
result
breakage
or
by-product
generation,
while
method
is
efficient
controllable,
allows
for
direct
salt
(potassium,
lithium,
sodium,
guanidine)
simply
changing
electrolyte.
Electrochemical
testing
situ
ATR-SEIRAS
analysis
showed
that
electro
M-AzTT
occurred
earlier
than
OER.
Therefore,
under
alkaline
conditions,
65%
yield
81.5%
Faraday
efficiency
were
achieved
at
1.7
V
vs.
RHE.
summary,
study
not
only
constructs
super
compounds,
but
also
represents
new
breakthrough
electrochemistry
field
materials.
