Applied Surface Science 255 (2009) 81838189

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Pyrolysis of cellulose and lignin

T. Haensel a,*, A. Comouth a, P. Lorenz a, S. I.-U. Ahmed a, S. Krischok a, N. Zydziak b, A. Kauffmann b,
J.A. Schaefer a
a
b

Institut fur Physik and Institut fur Mikro- und Nanotechnologien, Technische Universitat Ilmenau, P.O. Box 100565, 98684 Ilmenau, Germany
Fraunhofer Institute for Chemical Technology, Joseph-von-Fraunhofer-Str. 7, 76327 Pnztal (Berghausen), Germany

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 12 March 2009
Received in revised form 19 May 2009
Accepted 19 May 2009
Available online 27 May 2009

X-ray and UV-induced photoelectron spectroscopy (XPS and UPS) and scanning electron microscopy
(SEM) have been performed to characterise the pyrolysis of cellulose and lignin and their interaction
with methanol. Clean highly oriented pyrolitic graphite (HOPG) was also analysed as a reference
material. Asymmetric C1s core level ts and valence band XPS of the samples indicate a graphitic-like
structure after the pyrolysis at 1200  C. Due to the low polar contents in pyrolysed cellulose and lignin,
an interaction with methanol under high vacuum conditions could not be identied. From a technical
viewpoint a temperature of 1200  C is attainable without high costs. Therefore, the pyrolysis of woodbased polymers containing high amounts of cellulose and lignin are potential low-cost materials for
various applications. If it is possible to generate graphite in complex structures made of wood-based
polymers, a cheap and energy-efcient method will become available for producing bipolar plates for
fuel cells. Technical problems like form instability and foaming are discussed as well as further
development and possible modications of the ground material to achieve optimal compositions.
2009 Elsevier B.V. All rights reserved.

Keywords:
Cellulose
Lignin
Pyrolysis
XPS
UPS
HOPG
Valence band
Methanol
VB

1. Introduction
Direct methanol fuel cells are widely used for portable
applications [1]. One of the cost-intensive components is the
bipolar plate, which is typically made of graphite. It has the task to
separate anode and cathode and to conduct the current generated
in the fuel cell. Cheaper polymer compounds and composite
materials have been investigated for the use as bipolar plates in
direct methanol fuel cells instead of graphite [2]. Cheap
processable wood-based compounds (ARBOFORM1) made of
cellulose, lignin and additives are possible alternatives, because
the resistance can be decreased with a pyrolysis process. Such
wood-based materials are possible alternatives to synthesized
plastics [3]. Methanol is regarded to be one important energy
storage possibility for the future [4]. The direct conversion of
chemical energy into electrical energy with fuel cells is an effective
way to solve energy problems. Especially for portable applications
like mobile phones and laptops, the direct methanol fuel cell
(DMFC) is a viable alternative to conventional storage methods.
From a technical point of view there are some challenges, such as
current efciency, which keeps industry away from using DMFCs

* Corresponding author.
E-mail address: thomas.haensel@tu-ilmenau.de (T. Haensel).
0169-4332/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2009.05.047

on a large scale. The high cost of the DMFCs are also limitating
factors. Within the DMFC, a cost and energy intensive component
is the bipolar plate, which conventionally consists of graphite.
Especially the complex shape with the presence of uid channels of
this component causes material and time losses, because tracks for
uid ow must be established by milling [2]. As the main
requirement of this part is the non-permeability to reacting gases
and the electrical conductivity, a cheaper solution is desirable.
Metals like stainless steel, coated metals (also with gold), titanium
and other materials are possible alternatives [2]. It is also believed,
that injection moulded polymer plates with contents of conductive
additions like carbon nanotubes can replace graphite bipolar
plates, as they are also made of carbon. A novel idea is to injection
mould wood-based polymer plates and pyrolyse them to increase
the conductivity. However, there are some technical challenges
occurring during the pyrolysis, like shape distortion, lumps and
brittleness [5], which have to be solved to obtain a cheap and light
alternative material. Thus, one of the biggest challenges is to
understand pyrolysis of this material.
It is difcult to investigate what happens during the pyrolysis of
this complex system. It has been predicted that fractional
graphitisation of wood-based materials occurs [4]. A mass loss
of about 70% takes place after pyrolysis at 1200  C. It is clear that
not only does oxygen desorb and a graphitic structure remain, but
in fact, CO and complex carbon compounds are released. In this

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T. Haensel et al. / Applied Surface Science 255 (2009) 81838189

process, it seems to be unclear whether the OH-groups of cellulose

or the monomers are cracked during pyrolysis under low
temperatures up to 600  C.
Due to the complex structure of the compounds basic research
is needed for the main constituents cellulose and lignin. Using XPS
and UPS as a surface sensitive method (information depth about
10 nm), it is possible to investigate the binding relations of the
complex structures of cellulose [68] and lignin in their native as
well as pyrolysed states. Charging effects of the insulting lignin and
cellulose have to be discussed, but the peak shape does not change
drastically by FWHM optimisation on C1s- or O1s-peak. Therefore,
a qualitative analysis is still possible.
2. Experimental
Commercially available cellulose lter papers from ROTH
(Rotilabo1-Rundlter, ltration time 100 s) and lignin powder
(alkali, average MW 28,000 from SigmaAldrich) were used as
cellulose and lignin samples, respectively.

The samples were pyrolysed in a conventional tube oven at

temperatures ranging from 600 to 1200  C. The pyrolysis was
terminated after a few minutes, when it was observed that the
samples do not degas anymore.
The samples were analysed in ultra high vacuum (pressure
below 109 mbar) with X-ray photoelectron spectroscopy (X-ray
source 10-610 Physical Electronics, monochromator PHI 10-60E,
analyser EA125, 7 channeltrons) and in high vacuum (pressure
about 107 mbar) with secondary electron microscopy (FEI, XL 30).
In the load lock of the used UHV chamber the samples degas in a
pressure range between 105 and 106 mbar. For the characterisation with X-ray photoelectron spectroscopy (XPS) we used
monochromatic Al K a radiation (U B 14 kV, P 300 W), whereas
for ultraviolet photoelectron spectroscopy (UPS) He II radiation
(40.8 eV) provided by He discharge lamp was used. The X-ray line
width of monochromatic Al K a radiation is below 300 meV. The
overall resolution (measured for the Ag3d5/2 peak) is 0.56 and
1.15 eV at pass energies of 15 and 50 eV, respectively. More details
on the used experimental setup can be found elsewhere [9,10]. A

Fig. 1. (af) C1s and O1s photoelectron spectra of pure and pyrolysed cellulose (600 and 1200  C). The chemical shifts indicate pyrolysis process-related changes of the
functional groups in the samples. Note that the C1s (CC/CH) peak is asymmetric like in graphite after pyrolysis (1200  C).

T. Haensel et al. / Applied Surface Science 255 (2009) 81838189

commercial neutraliser (Omicron CN 10) was implemented to

compensate for charging effects of the insulating samples. All
spectra are recorded with an emission angle of 53 with respect to
the surface normal, ensuring optimum operating conditions for the
neutraliser for geometrical reasons. By varying the deection, the
electron beam energy and the current, the FWHM of the C1s peak
for the spectra of this sample was minimised to reduce the
broadening due to charging. One has to take into account that the
neutralisation process changes the sample potential causing the
binding energies of core level peaks and valence band structures to
shift [11].
The interaction of cellulose and lignin with methanol was
studied in the UHV chamber after introduction of methanol (purity
99.8%) at p  5  102 mbar for 1 min in the load lock. Prior
exposure of the samples via backlling the UHV chamber the
methanol was cleaned by several pump-freeze-cycles using liquid
nitrogen. All measurements were performed at room temperature.
Peak tting procedure was performed with the program
XPSPeak (version 4.1). The CC peak was set to 285 eV and the
functional groups were tted with peak shifts according to
literature within an error value of about 0:1 eV. A Shirley
background was applied in each case. The FWHM of the tted
peaks was set to the same value for each identical core level peak.
The artefact peak was not restricted in any way during peak tting.
3. Results and discussion
3.1. XPS
Cellulose and lignin consist of carbon, hydrogen and oxygen.
The C1s peaks of the XPS spectra were tted using various carbon
components (as indicated in Fig. 1). The chemical shifts were
interpretated according to the references. For charge compensation the CC binding peak was set to a binding energy of 285 eV to

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Table 1
Peakshift from CC peak to the C1s peak of HOPG with the binding energy of 285 eV,
C:O fraction and carbon content for the different samples (both atomic
concentration).
Sample

Peakshift [eV]

C:O

C content

Cellulose
Cellulose 600  C
Cellulose 1200  C
Lignin
Lignin 1200  C

0.56
2.65
0.3
2.23
0.31

1.1
6.8
14.0
6.2
29.7

0.53
0.87
0.93
0.86
0.97

compare changes occurring in the O1s peak and the valence band
structure. The chemical composition of the near surface region was
determined with the presumption of a uniform intermixing of the
components. For cellulose, the CC binding peak was subtracted
from the area of the C1s to determine the relative carbon to oxygen
content (Table 1), as there is no CC binding in pure cellulose. This
includes the presumption that this peak is caused by surface
impurities and a carbon rich contamination is present at the
surface of cellulose, but it ts very well to the theoretical C/O-ratio
of 6/5. However, other contributions may also be present. The data
suggest that they are present only in trace amounts because
otherwise the O/C-ratio would not reect that of pure cellulose.
Also, the ratio of the OCO/CC O peak area at 287.9 eV divided
by the CCO peak area at 286.5 eV is about 0.2, which is in very
good agreement with the chemical structure of cellulose. The tted
CC fraction may be caused by the production process, where the
CC-rich lignin has to be separated from cellulose [7].
The pyrolysis initiates a cracking process in cellulose and lignin
where more oxygen than carbon is released. This desorption is
preferential at higher temperatures and is not complete after a
pyrolysis at 600  C, because a higher carbon content of 0.93
compared to 0.87 is observed at 1200  C for cellulose. In addition,

Fig. 2. (ad) C1s and O1s photoelectron spectra of pure and pyrolysed lignin (1200  C). The chemical shifts indicate pyrolysis process-related changes of the functional groups
in the samples. The C1s (CC/CH) peak is asymmetric like in graphite after pyrolysis (1200  C).

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Fig. 3. (a and b) Valence band photoemission spectra of pure and pyrolysed cellulose and lignin compared to graphite (HOPG [14]). As a ngerprint of the electronic structure
the valence band indicates a graphitisation of cellulose and lignin after pyrolysis at 1200  C as the structure is nearly the same like HOPG. Lignin has a higher graphitisation
degree than cellulose after pyrolysis at 1200  C which can be seen in the O2s-shoulder at a binding energy of about 26 eV. Cellulose VB states taken from Danielache et al. [8].

smoke was released by the sample immediately upon annealing.

This is an indication that further degassing occurs. This smoke
release does not occur continuously but only when the temperature is increased.
By comparing the XPS C1s spectra of the natural and pyrolysed
cellulose and lignin one can clearly see an increase in the CCbinding fraction. The tting procedure for the O1s-peak cannot be
performed with consistent tting parameters. In literature the C1s
peak is often shown with the t parameters, but the O1s peaks are
discussed only rarely. The main problem is the small peak shift
between the COC and COH of about 0.6 eV [6,12], that is hard
to resolve with a spectrometer with a FWHM of about 0.6 eV.
Additionally, the peaks are broadened due to charging effects.
Another problem is the binding energy, which in itself cannot be
determined clearly after measurement with a neutraliser, also
varies for the same functional group, but belonging to different
polymers [12]. The sample potential was changed due to the slow
electrons and, therefore, the peaks where shifted. In principle, all
peaks should be shifted by the same offset, but the measurements
demonstrate that there is a difference between the FWHM
optimisation process on C1s and O1s with regard to the
displacement of C1s- and O1s-peak, respectively. This problem
is not fully understood yet, but it can explain the problem why it is
critical to determine the exact binding energy of the different O1s
components. However, the peak shape does not change drastically
when optimising using the C1s-states in comparison to the
optimisation on the O1s-states; only a displacement occurs. In our
study we used the C1s-optimised spectra for the tting procedure.
There are a number of papers about tting C1s peaks of cellulose
and similar polymers [7,12,13]. Small differences in the chemical
shifts of functional groups (about 0.2 eV) are possible. The C1s CC
binding energy peak is xed at 285 eV, the CO peak is tted with a
shift of about 1.5 eV and the C O/OCO peak is shifted from 2.8 to
3.1 eV with respect to the CC emission to higher binding energies.
Due to the neutralisation process, signicant Gauss broadening can
be observed and the GaussLorentz-ratio (G/L) was left unxed for
a better t under the conditions that every peak has the same G/Lratio. Moreover, due to neutralisation with slow electrons, a small
negative potential was induced on the sample surface. This means
that one has to take an artefact peak into account in the right
shoulder of the core level peaks. The intensity of that artefact
depends on the neutralisation process. These artefact peaks can be
seen in Figs. 1ad and 2a, b occurring due to the neutralisation
process. As the neutralisation was not applied for cellulose and
lignin pyrolysed at 1200  C, there should be no artefact peak in the

spectrum shown in Fig. 1f. In fact, a small peak named O3 is shown

in the O1s peak of cellulose (Fig. 1f). The origin of this peak is not
clear. One possible explanation is that it originates due to air
exposure.
Results show that the O1s peak broadens, as the FWHM is much
higher than that of the C1s peak (Figs. 1 and 2). This effect cannot
be explained with the neutralisation process, as the FWHM is
nearly the same in the O1s peak, when the sample was neutralised
with respect to the O1s peak. There might be more than two O1s
shifted states. However, the spectra can be tted with two main
states having a shift of about 1.5 eV between them. One possible
set of candidates for the O1 and O2 states could be the oxygen
present in COC and O CO, respectively. This will be examined
more closely in future studies. Only lignin cannot be tted with
two peaks. Based on the known structure of lignin 3 main oxygen
bonding environments are possible: oxygen single bonds between
carboncarbon bondings, oxygen single bonds next to carbon
oxygen bondings and terminal oxygen double bonds like in
carboxylic groups. In literature such strong shifts of about 2.1 eV
are reported to occur between an oxygen bonded between two

Fig. 4. UPS spectrum of pyrolysed cellulose and pyrolysed lignin (1200  C)

compared with HOPG. One can see a similar UPS spectrum of pyrolysed lignin like
HOPG. The smearing of the peaks are likely caused to the amorphous structure and
therefore a k-vector integrated graphite-like spectrum was measured for the
pyrolysed lignin.

T. Haensel et al. / Applied Surface Science 255 (2009) 81838189

phenol rings and the O C of a carboxylic group in poly(ether ether

ketone) (PEEK) [6]. These three functional groups are also part in
the amorphous structure of lignin, which is used for tting the O1s
structure. The FWHM of the tted peaks of about 2.75 eV in Fig. 2b
indicates a strong broadening mainly due to the neutralisation
process.
To extract more information about the electronic structure, XPS
VB spectra were measured. The VB structure of cellulose is in good
agreement with literature [6,7], and also with DFT-calculations [8].
Due to the fact, that lignin has more or less an amorphous structure
made up of three molecules, a wide range of lignin polymers exist.

8187

Consequently, it is difcult to compare this spectrum with other

lignin structures reported in literature.
Comparing the VB spectra from HOPG, which are in good
agreement with those reported in literature [14] with pyrolysed
cellulose and pyrolysed lignin (Fig. 3), one can clearly see trends in
the curve progression. Due to the fact that the VB structure is
correlated to the electric behaviour of a component, pyrolysed
lignin and pyrolysed cellulose possesses similar electric behaviour like graphite. Furthermore, one can say that the pyrolysis
of lignin and cellulose at 1200  C generates graphitic-like
structures.

Fig. 5. (af) Surface sensitive XPS measurements from pyrolysed cellulose and pyrolysed lignin (1200  C) as loaded and after methanol exposure. A chemical irreversible
reaction does not occur under room temperature UHV conditions.

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T. Haensel et al. / Applied Surface Science 255 (2009) 81838189

Fig. 6. (ac) SEM images from natural (a) and pyrolysed cellulose ((b) 600  C and (c) 1200  C). It can be seen that the bre structure thins down at higher pyrolysis
temperature.

3.2. UPS
UPS sources usually provide a high radiation intensity. As a
result, charging effects are very intense and compensation is
complicated due to the fact that the VB structure for these samples
is unknown. For this reason only pyrolysed samples, which are
conductive, can be measured (Fig. 4).
Comparing the UPS VB spectrum of pyrolysed lignin (1200  C)
and HOPG, one can identify VB peaks of HOPG in the pyrolysed
structure. However, the observed structures are not as pronounced
as for the HOPG. This might be caused, by the non-perfect
graphitisation, as e.g. indicated by some trace amounts of oxygen
and some minor carbon components besides the CC main peak in
XPS. In addition, due to the amorphous structure, most likely
disordered graphite-like structures are generated. This disordered
structure could explain the observed features in UPS in which a kvector integrated spectrum due to the randomly oriented graphitelike structure is measured. This phenomena will be further
examined in future studies. According to this interpretation, the
pyrolysis temperature of about 1200  C is probably not high
enough to generate oriented graphite structures made from lignin.
3.3. Interaction with methanol

The mass loss is about (95  1)% after annealing cellulose up to

600  C and (97  2)% after 1200  C measured with a precision
balance. Due to the fact that lignin has less oxygen content, the mass
loss of lignin during pyrolysis (1200  C) is only about 70%. In contrast
to cellulose, lignin bloats out and becomes visibly spongy, brittle and
cavernous in structure. This suggests that cellulose is a useful
material for imparting form stability while lignin is a better ground
material for forming graphitic-like structures, because undergoes
less material loss and the VB-spectra indicates a smaller oxygen
content after pyrolysis. Thus, in wood-based compounds for
pyrolysis it is necessary to have a mixture of cellulose and lignin.
4. Conclusions
XPS spectra clearly show a decrease of the oxygen content from
cellulose and lignin due to pyrolysis. The discussion of the binding
relations of the functional groups in C1s (OCO, CO, CC, O
C O) and O1s (C O, COC, COH) can be tted although the
same tting procedure cannot be applied to the measurements for
pyrolysed cellulose, pure and pyrolysed lignin at the same time.
The asymmetry of the CC content in the C1s peak and the XPS VB
structure indicates a graphitic structure of the pyrolysed cellulose
and pyrolysed lignin. The residual oxygen can be identied in the
O1s peak, but also in outlines the O2s broadening and is shifted
towards smaller binding energies. For samples used in this study,
the pyrolysis of cellulose and lignin at 1200  C generates graphitic
structures, but the pyrolysis is not complete. Comparing the UPS
spectrum of pyrolysed lignin and HOPG, it seems that randomly
oriented graphitic substructures are generated. Pyrolysed lignin
has a higher carbon content, indicating that lignin is a better basic
raw material for generating graphitic structures. Weight measurements indicate a higher mass loss of cellulose (about 97%) instead
of lignin (about 70%) after pyrolysis at 1200  C. The pyrolysed
cellulose and pyrolysed lignin (1200  C) does not react with
methanol under the pressure conditions used. Pyrolysed woodbased compounds mainly consisting of lignin and cellulose are
potential low-cost bipolar plate material alternatives for graphite.
With a complex pyrolysis process foaming and form instabilities
can be considerably minimised, but the mass loss cannot be
reduced below 70% at 1200  C. Therefore, the pyrolysis process and
the composition (celluloselignin mixture) need to be optimised to
achieve more complete graphitisation.

The surface interaction of methanol with pyrolysed cellulose

and lignin (1200  C) was analysed by comparing the C1s-, O1s- and
VB-spectra before and after exposure to methanol in the load-lock
system ( p  5  102 mbar, duration about 1 min corresponding
to about 160 kL CH3OH). The peak shape before and after methanol
exposure does not change appreciably for the 1200  C-pyrolysed
samples (Fig. 5). Due to the surface sensitive XPS measurement one
can exclude an irreversible chemical reaction of methanol with the
analysed samples under these conditions. The emission angle of
53 results an information depth resolution of the C1s spectrum of
a few nanometers. A typical indication of methanol adsorption is
the presence of oxygen on the surface, as has been shown in
reference [15]. This can be detected using XPS with an estimated
resolution of 0.04 monolayers on a polymer (PE). While it is not
possible to exclude the adsorption process, it can be assumed that
any such process is not stable under UHV pressures. Especially the
chemical resistance of the pyrolysed samples afrms cellulose and
lignin as potential main components in bipolar plates for the use in
DMFCs.
Even though the methanol conditions applied in this study do
not represent the precise operation conditions in the DMFC, it is
still a useful preliminary test. Measurements performed after
exposing the samples to methanol, which is closer to operation
conditions (120  C, increased pressure) in a DMFC are planned.

The authors thank Annette Laffert for the support during the
measurements. This research was supported by the BMBF through
the project Arbopyrnet (FKZ:03SF0313).

3.4. SEM

References

Scanning electron microscopy (SEM) was performed to obtain

an overview about the structure of pure and pyrolysed cellulose
(Fig. 6), since drastic changes upon pyrolysis would not be
favorable for the DMFC application mentioned in the motivation.

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