metal oxides 4-7) via chemical reactions. Except the first modified carbon electrodes ... modified glassy carbon 3) and metal ..... on the alkylamide surfaces.
CHEMISTRY LETTERS,
pp.
361-366,
ORGANO-MODIFIED
1977.
Published
CARBON ELECTRODES.
by
I.
VIA AMIDE BONDS BY CAPACITANCE Masamichi
FUJIHIRA,
Pharmaceutical
The carbon of
electrodes
double
Since ical
the
the
become
lent metal by
of of
Miller
4-7) and
the
chemical
via
as species
only
3-7)
to
bound
parative tion on
work. 2) Also, there has been no report the double layer capacitance except our
the
6)
modified
spite
of
its
electrodes.
carbon
electrodes
of
modified
the
in
caused carbon
amino
In
this
by
the
acids
via
importance
as
paper,
the
and
bonds
one
of
modification
be
on
the
the
surface
succeeded
and
in
described
co-
their
pre-
modificaSnO2
properties layer
as
to
4-7) These and electro-
of the chemical of the modified
double
as and
far
Miller
electrochemical
of
will
and
effect paper
the
change
thus
electrodes. Auger, 5) though
2,3)
electrodes
employed
report
covasuch
carbon
carbon
been
chemistry,
of the previous
of
modified
chem-
through groups,
surface
no
the electrodes
prepared
important the
been
deter-
catalytic
been
has
amide
to
co-workers,2)
metal oxide by ESCA,3-7)
has
workers
active
and
first
amidation
The
useful
ESCA analysis.
have to
there
via
be
selective
3) and detail
of
optically
as
chemistry
date
electrodes
to
Miller
the
organosilane
However,
carbon
results
the
(ESCA).
functionally
studies
electrodes,
modified
with
by
Except
980
correlated
well
making
carbon in
Sendai
glassy
electrodes
reactions.
LAYER
modified
sensitizers7)
chemically modified glassy surfaces have been investigated
techniques.
of
Japan
chemically
proved
as
containing and
chemical
were
modified
of
OSA
spectroscopy
electrode
a means
ligands,3'4) 2)
been
modification
These
co-workers,
Aobayama,
have
a chiral
surfaces
2)
Tetsuo
University,
measurements
on
chemical
carbons,
oxides
prepare silanized
report
Society
OF MODIFIED
TAMURA, and
photoelectron
surface
interest.3-7)
attachment
asymmetric
of
STUDIES
of
bonds
X-ray
capacitance
first
of
amide by
extent
modification
has
via
Chemical
MEASUREMENTS AND ESCA1)
characteristics
analysis
layer
mine
Tohoku
electrochemical
surface
Akiko
Institute,
the
of
capacitance
well
as
of
ESCA spectra
surfaces.
EXPERIMENTAL The × 2mm One
end
finer μ.
glassy plate of
one After
zene
baked
oxides
the
in
this the
procedure and
direct
were
co-workers. dehydrative
dicyclohexylcarbodiimide
air
air
to
of
carbon 160℃
of the
2)
to
2000)
a
36
a
mirror
quinones,
was
was
Carbon
Co.
× 5.5
mm
mm
by
polishing
always
amine
acid
and was
and
the to
surface form
the
a
water, on
17
mm
for
paper
by
1
μ and and
carbon
formation
amide
group linkage.
was
2)
sur-
surface
described
chloride,
carboxyl
ben-
of The
that
0.3
surface
lactones.8-10) acid
mm
(successively of
the to
× 17
ESCA.
ethanol, the
similar via
as plate
alumina
accompanied
procedure
employed
emery
with
alcohols, the
× 2
with
washed
electrodes
only
between
Tokai
carboxylic
phenolic carbon not
(DCC) 11,12)
The
mm
finish
by were
hr.
which
However,
17
followed
modified
coupling
from
as
specimens for
oxidation,
forms
and
surfaced
down
at
obtained
use
was
100
glassy in
by
synthetic Miller
specimen No.
polishing,
and
(GC-30S)
electrochemical
each from
introduced face
carbons for
but using
by also
362
Chemistry
The
cell
viously vacua
of
the
design
described.
6)
10-9
torr.
untreated
tilled RESULTS
and
types
(b)
an
surface
chloride,
acid
(e)
with An
an
ESCA
gether
with
the in
eV
which
to
several
α3α4, valence
the band
The
spectrum is peak
co-workers on
ance
of
by small
may
be
in
previously
of
groups dation
such as conditions,
change
in
will
treatment
C ls
similar used
to
with
peak
prepared
the
of
by
those
pre-
Mg anode
at
284.3
using
be of
peak
used
oxides
the
to
is
modifications
dry
C ls
determine
and
at
eV of
doubly
dis-
unbaked
sur-
surface
with
via
(f)
acid
an
amidated
in
Fig.
sur-
Further and
wet
the of
higher
532
eV
at In
but
bears
concluded
as
in
in
the
carbon
are
energy
side by
of
Mg
window, be noted
and
the
peak
the
the that
oxygen
the
after
heating to
by
This
air.
conditions electrodes.
will
clarify
for These
the
main On
agrees
the
The
C ls the
other appre-
the
functional the oxiand the
distribution
of and
oxidation will
by
that
the effect of binding energy
surface
of appear-
peak
with
alcohols,
results
of
The
surface
the
phenolic
is
indicates
the on in
carbon
shape
b.
oxidation.
This
characterize
acids,
the
oxides. the
the
and
cor-
Thomas
carbon
in a
the
by
glassy
type
oxidation
in
done
from
of
surface
profile peak
by
side
to
been
change of
of
resemblance
present
little
spectra
of
C ls
no the
energy
the
carboxylic
optimal
at
aluminum it should
photoelectron
very the
binding
peaks.
C ls
stimulated
having
work is now in progress methods, on the shift
as
to-
there
binding (D)
1,
resolution. and
addition,
higher
that
bonding
methods
and O ls such
be
formed
other
in
is
shows
formation
the
peaks
the
shown
surface.
Since
change of
C is
satellite
predominant,
the
is
from the However,
between
were
with
oxides
amidated
b)
13,14)
C ls
the
higher
to
half-width
of
an
n-octylamine
DCC,
for O
graphite,
carbon.
a marked
the
surface
(c)
but
(type
on
scan
can that
the
attributed showed
the
of
observed
on
and
(A,B)
this
it
bonded
surface
profile
a washed
with
referenced.
narrow
that
depth
obtained
the
the
Thus,
was
in
hr.,
160℃
the radiation literature.14)
carbon
sp3
titrations.8) both
(a)
using
peaks
α1α2,
on
as
escape
broad
increase
results
and
the
by the
in
14)
oxidation
peak
kinds
peak
than
36
N ls,
plasmon K
detectable
vitreous
but
the O ls
several
is
for
the
Mg
Kα) stimulated reported in
diamond.
rather
oxidation
variety
the
surface
strong were
to by
C ls
for
at
ls,
two
energies
asymmetrical in
within
peak
ciable
to
ESCA:
n-butylamine
of O
corresponding
15)
sp2
substratum C is
binding
of
air
baked
contains
nitrogen
carbon
the
was
was
by
amidated
carbon
stimulated
as
in
an
with
spectra
scan
all
C ls(Al (VB)
responding
hand,
200
DCC.
glassy
of
wide
peak
chemisorbed
based
were
ES
Solution
examined
160℃
(d)
surface
of
peaks
C ls
K
and
used
Model
referenced
13,14)
were at
using
insets
small
main
amidated
spectriun
spectrum
glassy
were
surfaces
via
n-octylamine
no
AEI
chemicals.
oxidized
face
the
an
electrode.
carbon
chloride,
284.3
carbon
equipment
analysis,
energies
G.R.-grade
of
n-butylamine
The
electrochemical
1977
AND DISCUSSION
Six face,
the ESCA
Binding
glassy
water
and For
Letters,
be
the
lactones as
reported
a pre-
Chemistry
Letters,
1977
363
elsewhere. The group (type which
change
on
the
c)
is
ESCA
oxidized in
almost
eV
of
accounts
Fig.
graphitic
that
the
modified
b)
where to
onto
carbon
to
(type
is
the
of
n-butylamine
c,
glassy
other
are
of
proved
to
(type introduction
shifted
energy
consist of
of
the
around is
two
glassy
acid
The
hydrocarbons
substratum
carboxyl
derivatives
surface
binding
C ls
surface via
omitted.
carbon
higher
the
derivative
of
type
the
of
c)
and
modification
spectra
of
the
energy
the
to
the
that
chains
hydrocarbons
with
(type 2,
binding
surface
overlaying
spectra
identical
hydrocarbon
284.3
C ls
carbon
shown
were
aliphatic
the
in
285
peaks
carbon
chloride d,
C ls
e,
and
of
linear
peak
284.5
eV.
Taking
eV,13)
the
C ls
attributable
from
the
f),
from into peak
to
of
the
deconvolution
anal-
ysis. As able as
a result
ESCA shown
(type
N ls
as the
the
surface
O ls
peak
is
can of
be
the
since
amidation of
3,
various
amide
around
a precursor
b)
band
peak
Fig.
for
the
the
in
N ls
linkage,
of
399.6
while
the of
kinds
the
the
modified
attributable
to
is
(type
From
d)
elimination
compared from
the
the
The
with known
that
of
binding
2.
1.
ESCA
spectra
of
oxidized
glassy
carbon.
-----
type
The caused
the
the
binding
The
profile
was
b
oxidized
alkylamidated
of
,
change
shown
in
by
by
of
of O ls
the
the O ls in
for
Fig.
4,
the
ESCA
C ls
modification
surface surface
- oxidized surface n-butylamidated
ESCA
amide
removed
as
of on
the
the
width
f)
surface
peak
of
the
c to
energies
nitrogen
energies
spectra of
of
(type
the
acids
appreci-
oxidized
introduction
decrease
Fig.
Fig.
known 16)
carboxylic
DCC.
the
expect.
by
an
surface
on the
we would
surface
with
modified
discernible
affected
the
or
surfaces,
compounds,
as
also
of
chloride
every
surfaces.
groups
was
derivatized
on
containing
amide
oxygen
the
hardly
modified
to
surface
on
observed
peak
nitrogen
surface
thionyl
such
N ls
of
hydroxyl
formation eV was
these
assigned
oxidized
with
bond
(type (type surface
b)
to c).
364
various
forms
of
Miller
oxygen.
and
doubtedly trodes ed
(type
(type
b)
binding
faces a
order the
when
fore,
the
mation
on
edge
a)in
surface.
potential
and SCE
the
ten
to at
5.
layer
modified
were was
of at
the
modifilower
oxidized of
electrode
the
charging
capacitance
caused
glassy
carbon
sur-
modified
SnO2
electrodes.
general
when
the
in
adsorbed
un-
elec-
apparently
the
conductive
and
in
32
between
CO and
in
the
moderate
avoid
such
graphite
physically
for
the
0.1
and
at
6)
surface
the
was
basal
CO2
to
at
N ls surfaces
spectra
of (type
oxidized c
-
f).
a
electrode
the
SCE.
(type
to
measure
the
covered
with
anodic
from
arising
in
the
the
determined
The
in in
4.
b) -----
the
the
The
oxidized
alkylamidated
to
21
3
V
for-
K2SO4,
the
μF/cm2
for
between 0.1
±
2
measured
carbon
μF/cm2
in
the
capacitance roughness.
change by
0.8
oxides
glassy
surface
caused
the
±
region
be
oxide There-
0.2
0.5M
35
untreated to
error
difference
be
potential
On
the
the
with
to
capacitance
-
from
in , contact
quantita-
potential.
region
Austin19)
minimal.
more
and high
potential
was
V vs.
oxidized
and
capacitance
0.8
employed
be
plane was
capacitance
complexity
Ateya
due
layer
electrodes
by
current
probably
to
evolve
to
μF/cm2
double
18)
known
estimated
work,
is
to
order
residual
the
co-workers
pyrolytic
± 3
in
are
and
was
present
percent
change
the
and
or
lowering
spectra
ESCA
It
types
showed
This
observed
of
3.
a)
highly
and
f)
double
Fig.
Fig.
to
chemically
is
six
voltammograms
c (type
the the
version. the
cyclic
Fig.
electrolyte
measured
On
where
region
about
the
electrodes
1M Na2SO4
vs.
to
Gileadi
was
plane V
(type
of Carbon
capacitance
atom
and 0.5
electrodes
unmodified
electrical
capacitance
the
anodized
the
in
the
observed
added
the
washed
shown
of
Helmholtz
are
double layer
modified
the
distinguish
(type
the
hydrocarbons
previously
capacitance aq.
as
decrease
investigate
6)
in
1977
.
method
they
SCE
observation
the
but
that
the
to
hydrocarbons at
2)
from study
observed
the
paper
appearance,
those
are
to
previously.
film
of
of
present
saturated
to
been
substances interfaces
tively,
their
their
voltammetry
the
nonconducting
having
In
vs.
due
lowering
active -solution
from
linear
in
sweep
in
their
be
or
also
than
the
as
described
eye
f)
against may
Such
to with
currents
currents
as
a
electrodes
charging
by
by impossible
Letters,
17)
co-workers
indistinguishable
Chemistry
in the
ESCA O ls
modification
surface surface
- oxidized surface n-octylamidated
The
(type (type surface
b)
to d).
Chemistry
Letters,
1977
was
measured
capacitance to
cathodic the
observed
than
and
0.8
V vs.
surface temperature Austin
SCE. showed
may be
cleaning
than
As in
case
with
density
specimen
may
modified
layers,
of be
while
basal
by
the
results
to
cut
out
chemical
carboxylic
since surfaces
plates
the
modifications,
5.
Cyclic
(type
a
and
(type
c
to
mV s-1.
though
voltammograms b)
f)
and in
modified 1M Na2SO4.
on
Scan
rate:
potensomewhat
increase at
of
the
the
higher by Ateya
pretreatment
by
edge on
and
for
Fig.
of
of the
lower
capac-
Therefore,
the
modifications.
energy
of
measured 5
The
17
C ls
at at
to
the
at
the
in
from
the
results
edges oxygen,
planes.
This
glassy
carbon
reaction
(type
a and
b)
electrodes
(type
c and
d).
triangular
wave:
50
mV p-p,
and
how
of the
and
supported
the
change
capacitance
unmodified
carbon
(probably
to
Differential
of
be
to of
8,14)
can
conditions
attributed
the
specimen
ESCA
chemisorbed
alkyl-
untreated
variation
and
peak
the
μF/cm2 on
oxidation
bound
somewhat
6.
surface
c). air
basal
much b).
capacitance
are
origin
is
gave
capacitance
from
than
the
from
the
the
and
rather
f)
a and
binding
the
oxides
fluctuation
electrodes
the
(type
free
both
of
of
of
surface
unmodified
V vs. was
the
was
obtained
capacitance
that
introduced
block) the
the
chloride
depended
carbon
the
the
c to
ranged
scattering
of
fluctuation
as
acid
essentially
to
0.8
between 0.2
oxidized
(type
and
of
via
are
of
region
during
extent
peak
good
acidic
to
difference
1M Na2SO4
capacitance
(type
the
capacitance
the
consist
from
judge
the
the
be due
surface
surfaces
ESCA N ls
acid
for
must
surfaces oxidized
so
0.2
19)
to
not
n-butylamine
surfaces
that the
and
-
little
in
potential
roughness
mV successively
direction b)
the
higher
100
from
different
the
The
surface
hydrogen.
example,
responsible
carbon
since
every
However,
(type in
at
measured 6).
capacitance
of
used
then
on
μF/cm2
reproducibility
however,
the
the
of
the
surfaces,
glassy
be
intensity
For
± 4
alkylamidated
can
was,
26
untreated
surfaces,
surface
surface
220
the
was
SCE
Fig.
surface
oxidation,
and
and in
capacitance.
the
the
surfaces.
amidated
Fig.
of
6)
V vs.
measured
oxidized
increase
0.2
lines
the
of
the
higher the
expect,
surfaces
oxidized
the
by
oxygen
of
modified
amidated
the
increase
measurements
the
the
or
The
to
those
capacitance
and
caused the
due
As we would
a
-
Fig.
results on
type
by evolving
itance
of
capacitance
of
roughness
in
to
(dashed
capacitance
that
0.8
lines
direction
the
The
from
(solid
anodic
between steps.
higher
first
potential
SCE along
tial
365
of modified
Superimposed 500
Hz.
in
the
366
Chemistry
the
yield
of
butyl
and
lower
than
of
the
amidation.
n-octylamidation, that
of
n-octylamide
often
by
age.
other
than the
hand,
the was
capacitance
results
are
shown
omitted
in to
gradually when the tial
Fig.
the
data
the
in
on
the
accord
alkylamide
capacitance
at
the
the
order
of
-
alkylamidated
0.2
and
electrodes
the
only
ESCA
using
was
analysis
results
derived
by
surfaces the poten-
SCE,
observed
DCC are
surfaces
from the Unless
V vs.
acid
DCC was
alkylamidated
0.8
aver-
between
capacitance
the
be layer
on
not
directly at
n-
reversed
routes
the alkyl group modified surfaces.
between
was
expectation
Typical
surfaces
the
between should
modification
capacitances
range
the
1977
Helmholtz
preparation
chloride.
due to the removal was applied on
potential
thicker
Though
chemical
acid
same
derivative
the
with
the
Accordingly,
the
lower
of
different
that
is
n-octylamide
one.
the
via
These
probably potential
the
because
appreciably.
modification
where
beyond
found showed
complication.
increased high anodic
in
the
6,
avoid
exceeded
change
as
not
modification
n-butylamide
by
DCC methods
well
of
were
and
as
of
results
the
the
derivative
difference
but
successful
of
capacitance
that
chloride also
extent
n-butylamide
fluctuation,
the
the
the
the
surface
the
On
If
Letters,
little
during
the
experiment. REFERENCES
1) This
work
ical 2)
was
chemistry,
5)
N.R.Armstrong,
6)
M.Fujihira,
7)
T.Osa
8)
H.P,Boehm,
9)
B.R.Puri,
and
J.C.Sheehan
12)
L.F.Fieser York,
13)
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15)
M.Barbar, K.Siegbahn Means Vol.
17)
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of 20
K.Siegbahn dam,
18)
M.Babai,
19)
B.G.Ateya
and
Physics
Y.,
1970,
and Y.,
Marcel
G.P.Hess,
J.
M.Fieser,
1976,
pp.
J.Hedman,
in
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(1976).
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