XPS Study of Hi ghl y Sul fonated Pol yani l i ne

X.-L. Wei
Chemical Physics Program, TheOhio StateUniversity, Columbus, Ohio 43210-1106
Mats Fahlman and A. J . Epstein
Departments of Physics and Chemistry, TheOhio StateUniversity, Columbus, Ohio 43210-1106
Received September 1, 1998
ABSTRACT: Hi ghl y sul fonated pol yani l i ne prepared vi a a syntheti c scheme usi ng l eucoemeral di ng base
(LEB-SPAN) has been studi ed usi ng X-ray photoel ectron spectroscopy (XPS). A sul fonati on l evel (
S
/N
rati o) as hi gh as 0.80 ( 0.10 has been reveal ed i n XPS anal ysi s, agreei ng wel l wi th the el ement chemi cal
anal ysi s resul ts (0.78). Thi s contrasts to an
S
/N rati o of 0.50 for SPAN made vi a the earl i er reported
syntheti c method. The detai l ed S 2p and N 1s peak anal yses both show that the oxi dati on l evel i s 50%,
i mpl yi ng a better thermal stabi l i ty of emeral di ne oxi dati on state over those of l eucoemeral di ne and
perni grani l i ne oxi dati on states. These XPS anal ysi s resul ts are supported by UV-vi s and FT-I R anal ysi s
resul ts. The method of resol vi ng 2p3/2 and 2p1/2 peaks i n the S 2p spectrum i s di scussed.
Introduction
XPS has been uti l i zed extensi vel y as an anal yti cal tool
to determi ne the chemi cal structures of pol yani l i ne
(PANI ; 1a-c)
1-5
because of i ts capabi l i ty of obtai ni ng
both the chemi cal composi ti on and oxi dati on state
i nformati on. I t has been especi al l y useful i n studi es of
both the sul fonati on and the dopi ng l evel of sul fonated
pol yani l i ne (SPAN; 1d).
1,5
Recentl y an al ternate syn-
theti c route for preparati on of hi ghl y sul fonated pol ya-
ni l i ne (LEB-SPAN
6
) has been devel oped by thi s group.
7
S
/
N
rati os as hi gh as 0.75 have been obtai ned, as
compared wi th 0.50 as the typi cal
S
/
N
rati o from other
syntheti c methods.
8
Novel physi cal properti es have been
measured and reported for LEB-SPAN, and a mecha-
ni sm has been proposed to account for the hi gher
sul fonati on l evel .
6
The hi gher sul fonati on l evel l eads to questi ons con-
cerni ng the oxi dati on state of the resul ti ng SPAN when
l eucoemeral di ne base (LEB) i s the starti ng materi al for
sul fonati on i nstead of the emeral di ne base (EB) and
perni grani l i ne base (PNB) forms of pol yani l i ne
8
and
whether al l of these ri ng-attached sul foni c aci ds sel f-
dope nearby i mi ne or ami ne ni trogen atoms. Though FT-
I R and UV-vi s data showed that the oxi dati on state i s
si mi l ar to that of the emeral di ne sal t,
6
these questi ons
remai ned to be answered more thoroughl y.
I n thi s paper, we address the questi ons by presenti ng
rel evant XPS anal ysi s resul ts for LEB-SPAN, provi di ng
di rect evi dence of a hi gher
S
/
N
rati o (>0.5), emeral di ne
oxi dati on state, and protonati on l evel .
Experimental Section
SamplePreparation. The syntheti c route of prepar-
i ng LEB-SPAN
7
i s bri efl y summari zed: EB (0.5 g)
prepared vi a a reported procedure
9
was pl aced i n a gl ass
mortar. Phenyl hydrazi ne (2.5 mL) was then added and
pressed wi th a gl ass pestl e for 5 mi n. Thi s mi xture
was sti rred for 1 h to al l ow EB to be reduced to LEB.
10
At the same ti me, 10 mL of fumi ng sul furi c aci d was
cool ed to 5 C for l ater use. The reduced EB (LEB)
was washed repeatedl y wi th ethyl ether and then
sucti on-dri ed. The dri ed LEB was sul fonated i n the 10
mL of precool ed fumi ng sul furi c aci d for 1 h, mai ntai n-
i ng the reacti on fl ask i n an i ce-water bath envi ron-
ment. The reacti on mi xture was subsequentl y i ntro-
duced i nto 0.75 L of 75:25 i ce-water mi xture to ensure
that the SPAN product was preci pi tated out. The SPAN
product was washed wi th three porti ons of 250 mL of
col d water, and the remai ni ng powder was dri ed uti l i z-
i ng the common procedure.
7,9
The LEB-SPAN powder
was pressed i nto pel l ets wi th a cl ean FTI R pel l et press
before bei ng i ntroduced i nto the XPS i nstrument cham-
ber.
Data Collection and Analysis. The XPS spectra
were col l ected on a VG SI MS-ESCA-ME system (model
no. SI M-ESCA-ME 1448) wi th Mg KR X-ray source
(1253.6 eV photons). The X-ray source was operated at
14 kV and 20 mA. The pol ymer powder sampl es were
mounted onto standard VG sampl e studs wi th doubl e-
si ded adhesi ve tapes and pumped i nto the preparati on
chamber to 10
-8
mbar before bei ng i ntroduced i nto the
XPS chamber. The pressure i n the XPS anal ysi s cham-
3114 Macromolecules 1999, 32, 3114-3117
10.1021/ma981386p CCC: $18.00 1999 Ameri can Chemi cal Soci ety
Publ i shed on Web 04/15/1999
ber was mai ntai ned at 10
-9
mbar or l ower duri ng
col l ecti on. The sampl e posi ti on and ti l t angl e (20 for
smal l -area XPS) were fi ne-tuned for opti mal data
acqui si ti on.
I n the data anal ysi s, the bi ndi ng energy (BE) of the
core l evel C 1s peak was set at 284.5 eV to compensate
for surface-chargi ng effects.
11
The Shi rl ey background
12
was subtracted and satel l i te peaks were removed for al l
el ement peaks before curve fi tti ng. The i terati on curve
fi t program (Levenberg-Marquardt method)
13
was cus-
tomi zed i n order to meet the speci fi c needs of resol vi ng
2p
3/2
and 2p
1/2
peaks i n the S 2p spectrum. The experi -
mental spectra were fi t i nto components of Gaussi an
l i ne shape.
14
The surface el emental composi ti ons were
determi ned by the rati os of peak areas corrected wi th
empi ri cal sensi ti vi ty factors.
11
Al l of the i ndi vi dual
spectra were smoothed wi th a three-poi nt averagi ng
routi ne.
Results and Discussion
Determination of Elemental Chemical Composi-
tion. The chemi cal composi ti on anal yses of LEB-SPAN
was determi ned uti l i zi ng both el emental chemi cal anal y-
si s
7
and XPS anal ysi s. A typi cal XPS data anal ysi s
yi el ds an
S
/
N
rati o of 0.80 ( 0.10. The experi mental
atomi c concentrati on i s C
6.12
N
1.00
S
0.80
O
2.53
, correspond-
i ng to an assumed formal formul a of (C
6
N)
1.00
H
3.50
-
(SO
3
H)
0.80
(CH
2
O)
0.12
. The smal l excess carbon and oxy-
gen i s assumed to be carbohydrate deposi ted on the
sampl e surface duri ng the XPS sampl e preparati on
process.
11
Thi s resul t i s consi stent wi th the el emental
chemi cal anal ysi s resul t, that i s, an
S
/
N
rati o of 0.78.
Anal . found: C, 46.9; N, 9.03; H, 3.01; S, 16.1; O, 25.0;
total , 100%. Cal cd: (C
6
)
1.00
N
0.99
H
3.73
(SO
3
H)
0.77
; total ,
99.1% (note that the measured oxygen content i s
determi ned by wei ght di fference).
Determination of Oxidation State and Doping
Level. The XPS spectra and the model fi ts are shown
i n Fi gures 1-4 for N 1s, S 2p, C 1s, and O 1s peaks,
respecti vel y. The opti mi zed parameters such as the fi t
component peak posi ti ons, peak wi dths, and area per-
centages are summari zed i n Tabl e 1. These spectra wi l l
be di scussed sequenti al l y bel ow.
Fi rst, the N 1s spectrum was fi tted smoothl y i nto four
component peaks. The 398.1 eV peak i s associ ated
1,4,5,15
wi th undoped i mi ne uni ts. The peak at 399.1 eV i s at
the same energy as that earl i er reported
1
for the N 1s
i n undoped ami ne uni ts. I n contrast, the 400.9 eV peak
i s associ ated wi th cati oni c ni trogen atoms (pol arons and
bi pol arons).
1,5,15
The 402.6 eV peak i s proposed to
correl ate wi th protonated ami ne uni ts whi ch are at a
hi gher bi ndi ng energy because of the stronger el ectron
l ocal i zati on associ ated wi th poorer conjugati on at sp
3
-
bonded si tes. Thei r percentages of the total N 1s
i ntensi ty are 398.1 (5%), 399.1 (38%), 400.9 (46%), and
402.6 eV (11%) peaks. The sum of the fracti on of cati oni c
ni trogen and undoped i mi ne si te for LEB-SPAN i s the
Figure 1. XPS N 1s core l evel spectrum. The fi t component
peaks are l abel ed i n the l egend box wi th thei r peak posi ti ons
i n el ectronvol ts.
Figure2. XPS S 2p core l evel spectrum. The fi tted component
peaks are l abel ed i n the l egend box wi th thei r peak posi ti ons
i n el ectronvol ts.
Figure3. XPS C 1s core l evel spectrum. The fi tted component
peaks are l abel ed i n l egend box wi th thei r peak posi ti ons i n
el ectronvol ts.
Macromolecules, Vol. 32, No. 9, 1999 XPS Study of Hi ghl y Sul fonated Pol yani l i ne 3115
same as those for EB-SPAN and PNB-SPANs, sup-
porti ng the cl ai m that LEB-SPAN i s sti l l i n the
emeral di ne oxi dati on state and i mpl yi ng that the em-
eral di ne oxi dati on state i s more stabl e than the other
oxi dati on states. However, a smal l porti on of i mi ne i s
not protonated, whi ch mi ght i mpl y that at the hi gher
sul fonati on l evel the protonati on may be more di ffi cul t
compared to the parent pol yani l i ne i n the ES form,
consi stent wi th sul fonati on l oweri ng the el ectron densi ty
at i mi ne ni trogen si tes. The hi gher
S
/
N
(l arger than 0.50)
mi ght be associ ated wi th parti al l y sul fonated ami ne,
whi ch supports the above assi gnments. I t was noted
1
that sul fonati on at the ri ng wi l l tend to l ocal i ze pol arons
due to the proxi mi ty of the SO
3
-
group to the chai n.
The S 2p spectra are fi t usi ng two doubl ets that refl ect
the S 2p spi n-orbi t i nteracti on (E 1.2 and the
rel ati ve i ntensi ty of spi n-up state, j )
3
/
2
, and spi n-down
state, j )
1
/
2
, are equal to 2).
11
The peak wi dths, the
peak energy separati on, and the peak i ntensi ty rati o of
the two components i n each doubl et are kept the same
duri ng si mul ati on whi l e the hei ght and the energy of
one component peak i n each doubl et are al l owed to vary
freel y. We propose the ori gi n of the two doubl ets are as
fol l ows: the doubl et wi th l ower BE i s from the sul fur
i n the ani on of the ri ng-attached sul foni c aci d that
protonates the ami ne ri ng uni ts or the i mi ne ri ng uni t,
l eadi ng to cati oni c ni trogen si tes. The doubl et wi th
hi gher BE i s from the sul fur i n neutral sul foni c aci d
substi tuents. The rati onal e for these assi gnments are
from fol l owi ng consi derati on: the sul fur i n the sul foni c
aci d groups protonati ng the ami ne or i mi ne ni trogens
menti oned above have a hi gher el ectron densi ty than
the neutral sul foni c aci d groups, -SO
3
H. The l ocal
el ectron densi ty on the sul fur atom refl ects i ts charge
and envi ronment and, therefore, i ts bi ndi ng energy.
On the basi s of the above assi gnments, i t i s found that
75% of -SO
3
H protonate the aromati c i mi ne and
ami ne and 25% are i n neutral substi tuent form.
Combi ni ng wi th the sul fonati on l evel (80%), these
dopi ng percentages of sul foni c aci d convert to doped
aromati c ami ne and i mi ne percentages, whi ch are l i sted
and compared wi th the percentages obtai ned from N 1s
peak anal ysi s i n Tabl e 2, where the undoped ami ne and
i mi ne are cal cul ated by di fference. I t i s seen that the
two sets of the percentages are sel f-consi stent, as wel l
as consi stent wi th the UV-vi s and FT-I R spectra
anal ysi s of LEB-SPAN.
6
The C 1s and O 1s spectra have uni que features. Both
peaks are smoothl y fi t as two component peaks, i ndi cat-
i ng that carbon as wel l as oxygen have di fferi ng chemi -
cal envi ronments among themsel ves, whi ch i s expected
to be true because as ri ng carbon atoms are attached
wi th several di fferent types of substi tuents whereas
oxygen atoms connect to di fferent sul fur atoms as
di scussed above. At the present ti me, the further
assi gnment of these two spectra are not pursued be-
cause the unavoi dabl e surface contami nati on of carbon
hydrates, (CH
2
O)
n
, though smal l , compl i cates the i n-
terpretati on.
Conclusion
The XPS anal yses of LEB-SPAN gi ven above show
that the LEB-SPAN i s i n the emeral di ne sal t oxi dati on
state and the sul fonati on l evel i s 80%, consi stent wi th
the UV-vi s, FT-I R, and el ement chemi cal anal ysi s
resul ts, i mpl yi ng a better thermal stabi l i ty of the
emeral di ne oxi dati on state than those of PNB and LEB.
The anal yses al so suggest that the aromati c ami ne are
parti al l y doped. On the other hand, a smal l porti on of
aromati c i mi ne i s not protonated because of the hi gh
sul fonati on l evel caused by el ectron densi ty defi ci ency.
The novel anal ysi s of S 2p spectrum i s sel f-consi stent
wi th the more tradi ti onal N 1s anal ysi s, provi di ng
supporti ng evi dence for the above concl usi ons.
Table 1. Binding Energies (eV) with Their Corresponding Atomic Concentrations and Peak Full Widths at Half
Maximum(in parentheses; area %and eV, respectively) of Various Charge-Corrected XPS Components of C 1s, N 1s,
O 1s, and S 2p Peaks
a
peak component 1 component 2 component 3 component 4
N 1s 398.1 (5, 2.0) 399.1 (38, 2.0) 400.9 (46, 2.0) 402.6 (11, 2.0)
S 2p 167.25 (75, 1.1) 168.55 (25, 1.1)
C 1s 284.5 (61, 2.4) 285.9 (39, 3.3)
O 1s 530.7 (30, 2.2) 531.5 (70, 3.5)
a
For brevi ty, onl y the bi ndi ng energy and the percentage of S 2p3/2 component of each doubl et are l i sted i n parentheses.
Figure4. XPS O 1s core l evel spectrum. The fi tted component
peaks are l abel ed i n l egend box wi th thei r peak posi ti ons i n
el ectronvol ts.
Table 2. Oxidation State and Doping Level in LEB-SPAN
Sample Obtained fromboth the N 1s and the S 2p XPS
Peak Analyses
a
peak
anal yzed
undoped (ami ne
and i mi ne)
doped
i mi ne
doped
ami ne
total
dopi ng
N 1s 43 46 11 57
S 2p 40 60
a
The S/N rati o used i n S 2p peak anal ysi s i s 0.8; the undoped
ami ne and i mi ne percentages are cal cul ated by percentage di ffer-
ence.
3116 Wei et al . Macromolecules, Vol. 32, No. 9, 1999
Acknowledgments. Thi s work has been supported
i n part by the U.S. Offi ce of Naval Research and the
Ai r Force Offi ce of Sci enti fi c Research.
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MA981386P
Macromolecules, Vol. 32, No. 9, 1999 XPS Study of Hi ghl y Sul fonated Pol yani l i ne 3117