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Photocatalytic removal of nitrogen oxides via titanium dioxide

Article  in  Environmental Chemistry Letters · December 2004


DOI: 10.1007/s10311-004-0087-2

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Environ Chem Lett (2004) 2:117–121
DOI 10.1007/s10311-004-0087-2

ORIGINAL PAPER

F. L. Toma · G. Bertrand · D. Klein · C. Coddet

Photocatalytic removal of nitrogen oxides via titanium dioxide

Received: 23 February 2003 / Accepted: 24 August 2004 / Published online: 23 October 2004
 Springer-Verlag 2004

Abstract We studied the removal of nitrogen oxides important role in atmospheric chemistry. NOx are emitted
pollutants via TiO2 Degussa P25 powder by photocatal- from natural sources, e.g. biological degradation in soil or
ysis. Parameters such as mass of catalyst, geometric ir- lighting thunder, and artificial sources, e.g. traffic, coal
radiated surface, catalyst morphology, and thermal treat- burning boilers, thermal power plants, and industrial and
ment were tested to explain the photocatalytic concen- chemical processes. The concentration of nitrogen oxides
tration decrease of nitrogen oxides. According to our in polluted urban air range is around 100 ppbv, whereas in
working conditions, the conversion rates increased until the unpolluted troposphere ranges from 10 to 500 pptv
an optimal value of the TiO2 weight, 35% of NO con- (Delany et al. 1982). Nitrogen oxides can have negative
centration and around 20% of NOx, was decomposed by effects on the ecosystems and man. Nitrogen oxides
the photocatalysis. The NOx removal increased propor- participate in the formation of acid rain, the greenhouse
tionally with the irradiated geometric surface. The struc- effect in synergy with sulphur oxides, and the photo-
tural transformation of anatase to rutile performed by chemical pollution in the presence of carbon monoxide
thermal treatment involved the decrease of the photocat- and volatile organic compounds. Regarding human
alytic activity. health, NOx causes problems in the respiratory tract in-
cluding, lung edema and the reduction of the oxygen
Keywords Photocatalysis · Titanium dioxide · Nitrogen caring capacity of the blood,e.g. the transformation of
oxides · Photocatalytic efficiency haemoglobin to methemoglobin.
Although the techniques of low NOx burners and se-
lective catalytic/non-catalytic reduction are the most
Introduction popular in regards to NOx decrease, the photocatalytic
methods gained much more attention in the oxidation and
Photocatalytic processes, which allow the decomposition removal of atmospheric nitrogen oxides. In this study, a
of organic compounds and removal of harmful gases, are photocatalytic test was performed focusing on the de-
among the most studied methods in solving the major crease of nitrogen oxides via titanium dioxide powder.
problems of air and water pollution (Ollis and Al-Ekabi Several parameters such as the mass of the catalyst, the
1993). Titanium dioxide is one of the major photocata- surface irradiated by ultraviolet light, the powder mor-
lysts used for such applications. The photocatalytic effi- phology and the crystalline phases were studied regarding
ciency of TiO2 depends on different parameters such as the photocatalytic removal of nitrogen oxides.
crystalline phase, surface morphology, specific surface
area, and thermal treatment (Tanaka et al. 1993; Fujishima
et al. 2000). Experimental
In this study, nitrogen oxides (NOx) are chosen be-
cause they are major atmospheric pollutants and play an TiO2 photocatalyst

F. L. Toma · G. Bertrand · D. Klein ()) · C. Coddet


TiO2 Degussa P25 powder from Degussa AG, commonly
Laboratoire d’Etudes et de Recherches sur les Matriaux considered as a reference for the evaluation of photocat-
les Procds et les Surfaces (LERMPS), alytic activity, was used to test the photocatalytic dimi-
Universit de Technologie de Belfort-Montbliard (UTBM), nution of nitrogen oxides. This powder has a specific
Site de Svenans, 90010 Belfort Cedex, France surface area of about 50 m2/g, determined by the nitrogen
e-mail: didier.klein@utbm.fr adsorption at 77 K. X-ray diffraction, performed with a
Tel.: +33-3-84583287 X’Pert MPD Philips diffractometer using Cu Ka radia-
Fax: +33-3-84583286
118

tion, was used to assess the anatase to rutile ratio. The decrease in the concentration of pollutants was obtained
volume percentage of anatase was determined according only in the presence of both photocatalyst and ultraviolet
to the following relation (Berger-Keller et al. 2003): light.
8IA The photocatalytic efficiency was evaluated after the
CA ¼ ð1Þ first 30 min of irradiation as a ratio of the removed
8IA þ 13IR concentration of nitrogen oxides. The conversion rates of
where IA and IR are the X-ray intensities of the anatase NO and NOx concentrations were calculated with the
(101) and the rutile (110) peaks, respectively. The crys- following relations:
tallite size was evaluated via the Scherrer formula. De- ðNOÞinitial  ðNOÞUV
gussa P25 is constituted of spherical nanoparticles of NOconversionð%Þ ¼  100 ð2aÞ
anatase phase (81.8 vol%) with a crystallite size of ðNOÞinitial
27.4 nm and rutile phase with crystallites of 50.2 nm, that
agglomerated in clusters of about 30 mm. ðNOxÞinitial  ðNOxÞUV
NOxconversionð%Þ ¼  100
ðNOxÞinitial
ð2bÞ
Photocatalytic set-up for the removal of nitrogen oxides
where “(NO)initial“ and “(NOx)initial“ are the NO and NOx
The photocatalytic decrease of nitrogen oxides was per- concentrations without irradiation; “(NO)UV“ and
formed in a test chamber built specifically for that pur- “(NOx)UV“ are the values of the NO and NOx concen-
pose (Toma et al. 2003). The experimental device consists trations under ultraviolet irradiation.
of three parts: a chamber where the gaseous nitrogen
oxides were prepared in situ by chemical reaction be-
tween copper powder and a dilute solution of nitric acid, Effect of catalyst mass
an environmental chamber, and a nitrogen oxides ana-
lyser. The pollutants were injected at room temperature The photocatalytic tests were performed with different
into the environmental chamber (volume of about 0.4 m3) amounts of TiO2 Degussa P25 powder, ranging from 0.01
until the volume concentration of nitrogen oxides reached to 1.2 g. The catalyst was uniformly exposed by me-
1–2 ppmv. A fan ensured the homogenization of gaseous chanical sieving (62-mm sieve opening) to ensure a ho-
pollutants into the environmental chamber. The photo- mogeneous repartition of the catalyst over the entire
catalytic reactor, a 10010050 mm polycarbonate box surface of plastic Petri dishes with different surface areas.
equipped with a 7070 mm Plexiglas window that permits The TiO2 powder was placed inside the photocatalytic
the light passage from a 15 W daylight lamp with ultra- reactor and top irradiated.
violet (UV) fraction through 30% UVA and 4% UVB in Figure 1A resumes the photocatalytic conversion rates
the spectrum was placed inside the environmental as a function of the catalyst mass when the TiO2 powders
chamber and crossed by the NOx flow (flow rate was were sieved on a 54-cm2 surface Petri dish. For small
0.6 L/min). After the passage through the photo-reactor, powder quantities, the conversion rates increased pro-
the nitrogen oxides concentrations were continuously portionally and reached a maximum value for 0.2 g of the
measured using an AC-30 M dual chamber chemilumi- catalyst. For higher TiO2 powder quantities, the decrease
nescence NOx analyser from Environmental SA, France, in the nitrogen oxides concentrations remained constant
and recorded on a computer using an acquisition data set- and independent of the TiO2 powder amount. The con-
up. version rates of the NO and NOx, after 30 min of ultra-
violet irradiation, were about 32–35% and 15–18% re-
spectively, when the mass of the catalyst varied from 0.2
Results and discussion to 1.2 g. If the conversion rate is expressed as a function
of the quantity of the catalyst to the unit of the irradiated
Preliminary study surface, it was found that photocatalytic conversion in
nitrogen oxides reached a maximum value of 3.7–4 mg/
We studied the removal of NOx by photocatalysis via cm2 of TiO2 Degussa P25 powder.
TiO2. Before performing the photocatalytic test, a blank Similar behaviours were illustrated by Zhang et al.
test was carried out without the photocatalyst. When the 1994 and Herrmann 1999 who noted that the photocata-
nitrogen oxides were passed through the reactor without lytic degradation rate of different aqueous pollutants in-
TiO2, no significant changes in the nitrogen oxides con- creased with catalyst mass until a maximum value (opti-
centrations were observed during ultraviolet irradiation. mum value) that was dependant on the TiO2 nature, the
These results show that the photoreactions between the photo-reactor geometry and working conditions was
nitrogen oxides did not take place in absence of the cat- reached. The optimum mass corresponds to the case
alyst. When TiO2 Degussa P25 powder was used, as soon where all TiO2 particles are irradiated and utilized in the
as the ultraviolet lamp was turned on, the concentrations photocatalysis. Herrmann 1999 explained that a screening
of the pollutants started to decrease rapidly; then the ni- effect occurred when higher powder quantities were used,
trogen oxides diminution became slower with time. The because the particles that are in excess can mask a part of
119

Fig. 2 Comparative decrease of the nitrogen oxides removal per-


formed on TiO2 in the form of powder and pellets (plane surface of
54 cm2)

Photocatalytic efficiency of the pellets

In the section below, we report the influence of the cat-


alyst morphology on the photocatalytic conversion rate.
The tests were performed with the same TiO2 powder that
was compressed into pellets with a compression force of
about 5kN (compression velocity was 0.50 mm/min) in
various dishes allowing us to obtain pellets with different
surfaces areas between 20 to 54 cm2.
The pellet mass was varied between 0.4 to 1.2 g. In the
photocatalytic tests, only one-side plane surface of the
Fig. 1 Evaluation of the photocatalytic conversion rates as a pellet was exposed to the ultraviolet light. The tests per-
function of A weight of TiO2 Degussa P25 powder (exposed sur- formed via the pellets show that their activities were
face of 54 cm2); B geometric irradiated surface (with 0.4 g of slightly lower than the TiO2 powder exposed on the same
catalyst)
surface, due to the difference in the developed surface
area (Fig. 2). For a pellet surface of about 54 cm2, around
the photoactive surface. In such a way, Byrne et al. 1998 28–30% of NO and 10–12% of NOx were converted by
quoted that the conversion rate in the degradation of photocatalysis. Furthermore, a pellet disposing of a higher
phenol via irradiated TiO2 decreased with the mass of the surface area lead to a better photocatalytic removal of the
photocatalyst. Another factor that can be taken into ac- nitrogen oxides concentration. The amount of compressed
count is the fact that when the TiO2 powder bed is im- TiO2 powder as well as the thickness of the pellet had
portant, the photons can not penetrate and excite all the little influence on the nitrogen oxides decomposition, thus
particles, especially the particles located at the bottom of only the upper surface exposed to ultraviolet light played
the powder layer. Indeed, the effect of the progressive a large part in the photocatalytic tests.
opacity and compactness of the catalyst bed makes the
light absorption difficult.
Figure 1B points out that a better decrease of the NO Influence of the crystalline phase
and NOx concentrations was obtained when the same
mass of catalyst was sieved on a Petri dish disposing of a To assess the influence of the crystalline phases on the
larger surface. The result is explained by the fact that the photocatalytic efficiency, the TiO2 Degussa P25 was an-
number of active sites is more important when the TiO2 nealed at different temperatures from 300 to 900 C for
particles are exposed via a higher irradiated surface. A 24 h in an electric furnace in ambient air and cooled at
linear dependence between the conversion rate and the room temperature.
illuminated surface was also noted. For the photocatalytic tests, the annealed TiO2 De-
gussa P25 powders were prepared in the same conditions
by mechanical sieving on a Petri dish of 54 cm2 as the raw
TiO2 powder. The photocatalytic conversion rates of heat
120

removal was obtained via nanoparticles of titanium di-


oxide disposing of higher specific surface area. Besides,
Matsuda et al. 2001 affirmed that the amount of NOx
removal is dependent on the specific surface area and the
ultrafine particles are preferable for the photocatalytic
decrease of nitrogen oxides.

Conclusion
An environmental test chamber was developed and used
to evaluate the photocatalytic properties of TiO2 Degussa
P25 powder with respect to nitrogen oxides removal. We
found that a limit of 4 mg/cm2 of TiO2 powder were
necessary to obtain a better photocatalytic conversion of
pollutants. A better removal of NOx was noticed on a
larger irradiated surface and the reactive surface of the
catalyst played a large part in the photocatalytic test.
Fig. 3 Influence of the TiO2 powder annealing conditions on the When only the rutile structure was presented, the photo-
photocatalytic conversion of nitrogen oxides catalytic conversion of NO and NOx was drastically de-
creased to 10 and 5%, respectively. The anatase showed
treated TiO2 were evaluated and compared with the initial better efficiency for the photocatalytic decrease of the
TiO2 Degussa P25 powder as reported in Fig. 3. It appears nitrogen oxides. Currently, studies are being performed to
that for treatment temperatures lower than 600 C, the evaluate the photocatalytic activities of other types of ti-
efficiency in the pollutants decomposition was around tanium dioxide powders that will be compared with TiO2
30% for NO and 15% for NOx. When the TiO2 powder Degussa P25.
was annealed at a temperature of 900 C, the efficiency
decreased drastically down to 10% for NO and 5% for Acknowledgements Thanks are due to Dr. Didier Robert (Labo-
NOx removal. Therefore the photocatalytic conversion ratoire de Chimie et Applications “Procds Propres et Environ-
nement”, Universit de Metz, France) for the scientific discussions
rates of the TiO2 powder depends on the temperature of and delivery of the TiO2 Degussa P25 powder. The authors are very
the thermal annealing. gratefull to Dr. Cathy Meunier (CREST-UFC Montbliard, France)
The annealed TiO2 powders were characterized by X- for carrying out the XRD powders analysis. The financial support
ray diffraction to observe modifications in the crystalline for the FL Toma PhD Thesis provided by the “Communaut
d’Agglomration du Pays de Montbliard” (France) is acknowl-
phase ratio and/or crystallite size with temperatures. For edged.
the TiO2 powder treated at 300 C, no significant differ-
ences were identified; the volume ratio of the anatase
phase was practically the same as the non-treated powder.
After a thermal treatment at 600 C, the percentage of
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