Topics in Catalysis Vols. 16/17, Nos.

14, 2001

433

Photo-assisted processes for improved catalytic activity and

selectivity of environmentally harmful emissions
Sten Ljungstrm , Dinko Chakarov, Johan Bergeld, Stefan Johansson and Bengt Kasemo
Competence Centre for Catalysis and Department for Applied Physics, Chalmers University of Technology and Gteborg University,
S-412 96 Gteborg, Sweden
E-mail: ljung@fy.chalmers.se

Photoenhanced activity of several supported noble metal/metal oxide combinations has been explored. Significant activity is observed
for supported Pt and Pd samples. Specifically, the so called light-off temperatures for CO oxidation are found to decrease upon illumination. Evidence for a photocatalytic non-thermal mechanism rather than a photo-assisted thermal process is found through the wavelength
dependence for CO oxidation on a Pt/alumina catalyst. The difficulty of separating real photocatalytic from other photo-assisted effects in
the case of porous samples is discussed.
KEY WORDS: CO oxidation; photocatalysis; suppported noble metal catalysts; emission cleaning

1. Introduction
Two major challenges in catalytic cleaning of car exhausts are (i) lower NOx emissions and (ii) reduced carbon
monoxide and hydrocarbon emissions during cold start [1].
The search for improved low temperature catalytic activity
of car exhaust catalysts is shared with a similar desire to
clean industrial gas emissions [2] and wastewater [3] at the
lowest possible temperatures. Low temperature activity reduces unwanted emissions due to side reactions, occurring
at higher temperatures, and provides substantial energy savings.
The basic reasons for the loss of catalytic activity at low
temperatures are either that the activation energy for the desired reaction step is too high to be overcome by thermal excitation, i.e., R exp(Ea /kb T ) becomes too small (where
R is the rate and Ea the apparent activation energy), or that
the catalyst surface is poisoned by some species, which must
be removed before the reaction can proceed. In the latter
case Ea is the activation energy for desorption of the poisoning species. A classical example is self-poisoning by CO on
Pt and Pd, blocking sites for O2 surface dissociation. Similar
self-poisoning can occur for some hydrocarbons (HC). The
self-poisoning occurs at all gas mixtures except at very large
O2 excess [4].
For thermally excited reactions the only viable strategy (if
external heating is excluded) is to find catalysts that have low
activation barriers for all important reaction steps, including
desorption at low temperature of all of the (self) poisoning
molecules. An alternative approach is to use non-thermal,
selective excitation, e.g., by forming transient radicals that
can react at low temperatures. Such promotion can be accomplished by energetic particles or fields. Examples are
photocatalysis, electrocatalysis and plasma discharges.
To whom correspondence should be addressed.

In the present work we are exploring the photoinduced,

non-thermal pathway for improved low temperature catalytic activity. Early exploratory results of this effect are
presented, obtained with supported Pt and Pd catalysts on
alumina, with CO oxidation as the model reaction. The preliminary nature of the results is emphasised.
2. Experimental
The experiments were performed in a tubular flow reactor
with on-line mass spectrometry (MS) for control of the reaction products described earlier [5]. Samples of two types of
catalysts were explored: 1.412 kg m3 of Pt and 0.77 kg m3
of Pd, both on an Al2 O3 washcoat applied on a cordiorite
monolith. The samples were cut at an oblique angle (i.e.,
not perpendicular to the monolith channels) from supported
monolith catalysts and cleaned and thermally activated following standard procedures [6]. The sample temperature is
controlled by external heating of the reaction cell and is directly measured by a thermocouple placed inside one of the
sample channels. The non-polarised photon source is a cw
lamp system based on a 100 W Hg arc lamp, and a combination of band-pass and cut-off filters [7]. The irradiation is
made through the UV transparent (quartz) reactor wall (figure 1) onto the surfaces in line-of-sight of the obliquely cut
sample. Only a fraction of the total catalyst internal area is
illuminated in this way. However, for the present purpose,
where we explore if there is a photocatalytic effect rather
than a photoinduced thermal effect this arrangement is sufficient.
The standard gas mixture used in most of the experiments
(except in the one where the CO/O2 ratio was varied) was
2% CO, 1.17% O2 and 96.8% Ar, i.e., a value slightly
above one. The variables in the experiments were: (i) the
photon flux (up to 1.25 W cm2 for non-filtered radiation),
(ii) the photon energy, selected between 1.55 and 5.5 eV or
1022-5528/01/0900-0433$19.50/0 2001 Plenum Publishing Corporation

434

S. Ljungstrm et al. / Photoenhanced activity of noble metal/metal oxide combinations

Figure 1. Experimental set-up with a tubular flow reactor and on-line mass
spectrometry control of the reaction products.

Figure 2. Normalised mass spectrometer signals for CO and CO2 as a

function of the catalyst temperature in dark and under irradiation with
28 mW cm2 photons, < 420 nm. The overlapping traces represent repeated measurements for better determination of the ignition temperature.

220 < < 800 nm, and (iii) the gas composition. The
experiments were performed under a slow constant flow of
the reactant gas mixture. The conversion of CO to CO2 was
measured several centimeters downstream of the catalyst by
a quartz capillary gas sampling probe feeding the sample gas
into a Balzers QMC 120 mass spectrometer, placed in a turbopumped vacuum system [5].

3. Results
The main result of this study is the observation of a strong
radiation effect on the reaction rate, applying moderate photon fluxes. The light-off temperature (defined as the temperature, T 50 , where 50% of the minority reactant specie (usually CO) has been converted to CO2 ) is lowered substantially
when the sample is irradiated. The observed values were
T = 80 5 and 55 5 C for the Pd and Pt samples, respectively. An example is shown in figure 2 where also T
is defined graphically.
In order to examine the origin (thermal or non-thermal) of
the irradiation effect we performed power- and wavelengthdependence measurements, and measurements at different
CO/O2 mixtures. These results are presented in figures 35.
3.1. Wavelength dependence
In order to explore the mechanism of the light induced
lowering of the light off temperature, and to determine the
threshold photon energy (if any) for the photon-related increased catalytic activity (figures 3) we used narrow bandpass filters ( = 10 nm). Specifically we measured light
off temperatures by applying approximately the same irradiation power, but delivered by photons with different energy.
Within the accuracy of the experiment we found the same
threshold photon energy for both samples: around 3.4 eV
(360 nm), figure 3. For comparison, this energy is much

Figure 3. Wavelength dependence of the photoninduced reduction of the ignition temperature. The measurements were performed with photon fluxes
restricted to maximum12 mW cm2 .

lower than the observed threshold energy for CO photodesorption from the Pt(111) surface (5.1 eV) [8], or for O2
gas-phase photodissociation (5.2 eV, 238 nm). However, the
value is higher than the threshold energy for photodissociation of O2 adsorbed on Pt(111), 2.95 eV or 420 nm [9].
Note that the data points in figure 3 would lie on a nearly
horizontal line if the illumination effect on T were of
purely thermal origin, since T is normalised to incident
power (variations in diffuse reflectance with wavelength are
expected to be fairly small, and definitely less than variance
among the data points). The clear threshold behaviour of the
increase of T versus photon energy is strong evidence of a
real, non-thermal photocatalytic effect.
3.2. Influence of gas mixture
An additional experiment was made, where the power and
wavelength distribution of the radiation was kept constant,
and only the CO/O2 mixing ratio was varied. For comparison, the same reaction without illumination was measured

S. Ljungstrm et al. / Photoenhanced activity of noble metal/metal oxide combinations

435

erage decreases, and the relative oxygen coverage increases,

as increases in the studied range of gas mixing. It is also
possible, however, that CO is the dominant surface species
over the whole range of values in view of its larger sticking
coefficient compared to O2 , and because we are not at pure
mass transport control.
3.3. Power dependence

Figure 4. Rate of CO to CO2 conversion with (+) and without () illumination, as a function of CO/O2 gas mixture.

The measured power dependence of T is fairly linear in

the applied power (figure 5). We analysed these data in the
following way: (i) First we assumed a purely thermal effect,
i.e., that the sole effect of the light was to heat the sample
and thereby increasing the rate of reaction in an Arrhenius
type manner. (ii) As an alternative we assumed a purely
non-thermal mechanism whereby the rate would increase
linearly with increasing photon flux, and be an additive effect to the thermal reaction. These models are represented
by the dashed and full curves in figure 3. Both models can,
within experimental uncertainty, explain the experiment and
therefore does not allow a conclusion about the mechanism
(note however that the wavelength dependence shown above
provided clear evidence for a non-thermal effect).

4. Discussion

Figure 5. Dependence of the ignition (light-off) temperature on photon intensity. Experimental points are compared with models for purely thermal
(dashed line) and purely photon induced mechanisms (see the text).

over the same gas mixing interval under otherwise identical

conditions.
The most important result of this experiment (figure 4)
is that the illumination effect has a clear dependence on gas
composition. T 50 is always lower with illumination than T 50
in the dark, but the illumination effect is stronger at oxygen
excess in the gas, i.e., at > 1, compared to CO excess.
Since the gas phase is transparent to the radiation, and since
the power and wavelength distribution were kept constant,
the observed effect is attributed to the different surface coverage compositions as the O2 /CO ratio is varied. As increases there is successively more O2 in the gas phase. Since
we were performing the measurements at T 50 (50% conversion), the conversion of CO and O2 to CO2 is quite fast (50%
conversion), and there are therefore significant concentration
gradients in the gas phase. Consequently the kinetic phase
transition [10] where the surface coverage changes from being CO dominated, to being oxygen dominated, is expected
to occur at lower in our experiment than under purely kinetic control. Therefore it is likely that the relative CO cov-

In the discussion we cannot be definitive about detailed

mechanistic interpretations, since additional data are needed,
in a better-defined experimental geometry and over a broader
T range than in the present experiment. For example, only
part of the sample surface is illuminated and the measurements are predominantly performed at T 50 , where significant gas phase gradients exist.
In spite of this the data provide strong evidence of a
real photocatalytic effect. For example, in spite of serious
scrutiny we cannot explain the wavelength dependence of
T (figure 3) as a thermal effect, and we also fail to explain
the variation of T with varying gas mixture (figure 4) in
terms of a thermal effect. These two observations (of which
the wavelength dependence is the most important) provide
the strongest evidence for a photocatalytic effect. The power
dependence in figure 5 is less discriminating in this respect.
Regarding the mechanism we briefly note that the dominant mechanistic event in photoinduced surface reactions
is photon excitation of hot electrons [4,7]. Thus the most
likely mechanism in the present case is that the photons excite hot electrons in the small Pt or Pd particles deposited on
Al2 O3 , which in turn activate some surface species (electron
excitation in Al2 O3 is not likely at the studied wavelengths
because of the large bandgap in Al2 O3 ). Considering that
the wavelength dependence measurements were made with
close to a stoichiometric CO/O2 mixture, the most likely surface specie is CO, since the CO sticking coefficient is much
larger than that for O2 (see above). Since the CO + O2
reaction is known to be poisoned by CO, but not by oxygen, a likely activation process is photoinduced desorption

436

S. Ljungstrm et al. / Photoenhanced activity of noble metal/metal oxide combinations

of CO. However, because the experiments are made at high

absolute pressure (compared to UHV-experiments), we cannot exclude weakly bound O2 molecules on the surface that
might be activated by the photoelectrons as well, especially
since it is well established that weakly bound O2 on clean
Pt at low temperatures can be photodissociated via photoexcited hot electrons [9]. The mechanism needs further
scrutiny, under conditions where the surface coverage situation is easier to deduce than in the present case.

Acknowledgement
This project was initiated by a fund from PREEMs Environmental Foundation (PREEMs miljstiftelse). The work is
also supported by, the Engineering Sciences Research Council (contract # 98-793) and the Competence Centre for Catalysis, funded by the Swedish National Energy Administration
and the member companies: AB Volvo, Johnson Matthey
CSD, Saab Automobile AB, Perstorp AB and MTC AB.

References
[1] P.L. Burk, J.K. Hochmuth, D.R.Anderson, S. Sung, A. Punke, U.
Dahle, S.J. Tauster, C.O. Tolentino and J. Rogalo, in: Catalysis and
Automotive Pollution Control III, eds. Frennet and J.M. Bastin (Elsevier, Berlin, 1995).
[2] G. Mabilon, D. Durand and M. Prigent, Surf. Sci. Catal. 71 569 (Elsevier, 1991).
[3] D.F. Ollis and H. Al-Ehal, Photocatalytic Purification of Water and
Air (Elsevier, Amsterdam, 1993).
[4] M. Skoglundh, L.O. Lwendahl and J.-E. Otterstedt, Appl. Catal. 77
(1991).
[5] S. Lundgren, K.-E. Keck and B. Kasemo, Rev. Sci. Instrum. 65 (1994)
2696.
[6] P. Lf and B. Kasemo, J. Catal. 130 181 (1991).
[7] D.V. Chakarov, L. sterlund, B. Hellsing, V. Zhdanov and B. Kasemo,
J. Chem. Phys. 106 (1997) 982.
[8] R.R. Cavanagh, J.D. Beckerle, M. Garasse, E.J. Heilweil and J.C.
Stephensson, Surf. Sci. 269/270 113 (1992).
[9] W.D. Mieher and W. Ho, J. Chem. Phys. 99 (1993) 9279.
[10] V.P. Zhdanov and B. Kasemo, Surf. Sci. Rep. 20 (1994) 111.