ARTICLE IN PRESS

Atmospheric Environment 42 (2008) 4101–4112

www.elsevier.com/locate/atmosenv

The influence of photocatalytic interior paints on indoor

air quality
Joonas Auvinen1, Leif Wirtanen
Department of Civil and Environmental Engineering, Helsinki University of Technology, P.O. Box 2100, 02015 TKK Espoo, Finland
Received 16 November 2007; received in revised form 17 January 2008; accepted 17 January 2008

Abstract

A clean indoor air is important for the well-being and health of people. Lately, new photocatalytic paints have been
launched on the market, which are claimed to have air-purifying effects. Photocatalysis initiates radical reactions. Radicals
are formed when a photocatalyst (e.g. TiO2) is subjected to radiation. Typical radicals are the hydroxyl radical (dOH) and
the superoxide radical (dO2 ). Radicals cause chain reactions, which degrade and decompose organic compounds. The end
products of these chain reactions are water and carbon dioxide, if the reactions are fully completed (mineralization). If
mineralization does not take place, then a great number of side products can be formed, whose properties are not well
understood. The side products of photocatalytic reactions can be permanent and stabile. The decomposition of indoor air
impurities on the surface of photocatalytic paints is not obvious. The ability of photocatalytic indoor paints to reduce
chemical indoor air impurities is the key issue of this study. Six different paints with different binder systems, such as lime,
polyorganic siloxane, silica sol–gel and organic binders, were examined. The experiments were divided into three topics:
degradation of an organic binder, photocatalytic decomposition of formaldehyde, and a volatile organic compound (VOC)
mixture consisting of five different indoor air VOCs. All tests were carried out in an environmental test chamber under
dynamic conditions. The test results indicate that many indoor pollutants are generated under normal- and UVA-light.
Typical compounds formed include formaldehyde, acetone, acetaldehyde, etc. A clear decrease of formaldehyde or the
VOC mixture concentration was not observed. All possibly generated compounds could not be collected or analyzed in this
research project, but the measurements show that photocatalytic reactions do not generate only carbon dioxide and water.
Photocatalytic decomposition of indoor air impurities can, however, produce many side products, which may be stabile
and harmful.
r 2008 Elsevier Ltd. All rights reserved.

Keywords: VOC; Formaldehyde; Photocatalysis; Interior paints; TiO2

1. Introduction

Photocatalysis and its benefits in purifying indoor

Corresponding author. Tel.: +358 985 773 526;
air has opened its use in different industrial
applications (Fujishima et al., 1999). Commonly
fax: +358 985 776 901.
E-mail addresses: joonas.auvinen@gmail.com (J. Auvinen),
used means of decreasing chemical and partly
leif.wirtanen@tkk.fi, leif.wirtanen@tikkurila.com (L. Wirtanen). biological impurities of indoor air include filters
1
Tel.: +358 985 773 397; fax: +358 985 776 901. for the incoming air and air cleaners based on, e.g.

1352-2310/$ - see front matter r 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.atmosenv.2008.01.031
 ARTICLE IN PRESS
4102 J. Auvinen, L. Wirtanen / Atmospheric Environment 42 (2008) 4101–4112
photocatalysis (Zhao et al., 2003). Many articles
have been published under the title photocatalysis,
photocatalytic degradation, and its mechanisms.
The goal of photocatalysis is to degrade or
decompose organic pollutants such as formalde-
hyde, volatile organic compounds (VOCs), bacteria,
other chemical substances, etc. under sufficient UV-
light. The functioning mechanism is linked to
commonly used nanoscale TiO2 (anatase), which
can act as a photocatalyst and form highly active
radicals from water and oxygen molecules. These
radicals then form long reduction and oxidation
reaction chains. After the chain reactions are
completed, the end products should be water and
carbon dioxide (Fig. 1) (Hoffman et al., 1995).
Photocatalytic effects have been mostly investi-
gated on pure photocatalysts, e.g. on TiO2. TiO2 is a
typical semiconductor having an energy gap of
3.2 eV (387 nm for anatase) between valence and
reduction bands. The key step in photocatalysis is
the formation of hole–electron pairs on irradiation
with UV-light (Linsebigler et al., 1995). These
hole–electron pairs form highly active radicals such
as hydroxyl radical (dOH), superoxide radical (dO 2)
and hydrogen peroxide radical (dOOH). All these
radicals can oxidize or reduce indoor contaminants
(Kolenko et al., 2005).
To increase the photocatalytic activity of coatings
used indoors, where the UV-light intensity is much
lower than outdoors, TiO2 can be doped with
foreign atoms. This is done to decrease the band gap
energy needed for the activation of the catalyst
(Hoffman et al., 1995).
Paints have traditionally been developed to
decorate and protect our environment (Brock
et al., 2000). Lately many paints described as
‘‘indoor air purifying’’ have been launched on the
Fig. 1. The activation and the photocatalytic mechanism of TiO2 (left), the whole photocatalytic process (Fujishima et al., 1999).
market. However, only a few scientific articles have
been published about photocatalytic paints and
coatings (Allen et al., 2005; Salthammer et al., 2006;
Celiker et al., 2006). Allen et al. (2005) studied the
influence of different photocatalytic TiO2-pigments
in several binder systems, such as PVC-alkyd,
acrylic, and polyester siloxane. They concluded that
nanosized anatase operates primarily as an effective
photocatalyst, but that the nanograde rutile form of
TiO2 has also photocatalytic properties. Their
results indicate that by using different types of
TiO2 the photocatalytic efficiency of the paint film
can be controlled. Salthammer et al. (2006) studied
the photocatalytic efficiency of two different types
of commercially available wall paints in a 1 m3 test
chamber with and without air exchange using
artificial daylight. They spiked the test chamber
with each target compound and measured the
concentration vs. time profile. The results indicate
that photocatalysis works well for formaldehyde
under static conditions, but not under dynamic
conditions. For typical VOCs under dynamic
conditions, no significant photocatalytic effect could
be observed. Celiker et al. (2006) prepared paints by
incorporating nanosized anatase into them. They
studied the performance of the paint films by using
methylene blue, rhodamine, and resazurin solutions
under different light sources. They concluded that
even sufficient sunlight irradiation is adequate for
photocatalytic activity of the paint film, even
though a UVA-lamp is the most effective.
The aim of this study is to gain more information
about the photocatalytic behaviour of paints and
how this affects the quality of indoor air. In this
article, information is given about the influence of
photocatalytic paints on indoor air pollutants and
the possible self-degrading behaviour of these
 ARTICLE IN PRESS
J. Auvinen, L. Wirtanen / Atmospheric Environment 42 (2008) 4101–4112 4103

paints. The age of the paint and the dependence of The object was to investigate if photocatalytic
the UVA-light intensity on the photocatalytic paints are active in indoor air conditions. Does
activity were additional parameters studied. photocatalysis decompose and destroy organic
binder material? What is the difference between
2. Experimental normal office-light and UVA-light conditions as far
as photocatalysis is concerned? How does the age of
2.1. Background the paint film affect its photocatalytic behaviour?
What kind of products and how much will the
Six photocatalytic interior paints with different photoactive coatings generate? Last but not least,
binder systems and one reference paint were tested what kind of total influence does photocatalytic
for their capability to purify indoor air (Table 1). paints have on different indoor air impurities, such
Three of the six photocatalytic paints and the as formaldehyde and VOCs? (Wolkoff et al., 1997).
reference paint were commercially available. The
binder systems of the commercial products were (A)
polyorganic-siloxane, (B) PVAc–ethene copolymer, 2.2. Materials
(C) styrene–acrylic copolymer, and the self-pro-
duced were (D) silica sol–gel, (E) lime and (F) See Table 1 for materials used in this study and
PVAc–ethene copolymer. also for their main characteristics.
Paints were tested on three different substrates:
glass, gypsum plaster, and polymer-modified plas- 2.2.1. Preparation of the paint films
ter. The experiments were divided into three The size of the substrate was 220 mm  280 mm
different sections:  3 mm. One photocatalytic paint and one refer-
ence paint were applied to the substrate using a
(1) photocatalytic degradation of the organic bin- roller. Thus all the paints, the average target dry
der, film thickness was 80 mm when calculated using the
(2) photocatalytic decomposition and removal of following equation:
formaldehyde,
(3) photocatalytic decomposition and removal of a ðT t  A  dÞ
Ppaint ¼ (1)
mixture of five different indoor air VOCs. ðV s  100Þ
where P is the amount of wet product applied (g), Tt
is the dry film thickness for testing (mm) (EN 927-1,
1996), A is the painted area (cm2), d is the density of
Table 1 the wet product (g cm3), and Vs is the solid content
Materials used in this study and their main characteristics
of the product (vol%).
Material Main characteristics Classification The freshly painted surfaces were stored 2 days in
dynamic environmental test chambers and the aged
Photocatalytic Water-borne, Commercial paints were stored first 1 month in normal light and
paint A polyorganic–siloxane
Photocatalytic Water-borne, silica sol–gel Research
3 months under true light (8 W, containing the
paint B formula whole spectrum of ordinary sun light) before the
Photocatalytic Water-borne, lime Research start of the experiments. The storing conditions
paint C formula were 2372 1C and RH ¼ 5075%.
Photocatalytic Water-borne, PVAc/ethene Research
paint D formula
Photocatalytic Water-borne, PVAc/ethene Commercial 2.2.2. Preparation of the plasters and substrates
paint E
Photocatalytic Water-borne, styrene acrylic Commercial
The water mixable plasters were prepared by
paint F using a mixer attached to a power drill according to
Reference paint Water-borne, PVAc/ethene Commercial the manufacturer’s recommendations. A uniform
Plaster A Gypsum binder, water Commercial layer of the plaster was applied onto a glass plate
mixable with a spatula. A stainless steel border was used
Plaster B Polymeric binder, water Commercial
mixable
to adjust the sample thickness to 3 mm. The
Glass-plate – – test specimens were weighed before and after
application.
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4104 J. Auvinen, L. Wirtanen / Atmospheric Environment 42 (2008) 4101–4112
2.3. Methods and analysis
The experiments were carried out in environ-
mental test chambers made in accordance to ISO
16000-9 (2006). The volume of the chambers was
27 dm3 and the conditions were: temperature
2172 1C, relative humidity 5075%, air exchange
rate 0.5 h1. The loading of the chambers was
2.28 m2 m3. The chambers were cleaned before
each test; metal objects were cleaned in a hot
oven (t ¼ 400 1C) for 10 min and other surfaces
were cleaned with ethanol and water. The effective-
ness of the cleaning process was controlled by
measuring the blank value of each chamber before
every test. The blank values for VOCs were
o10 mg m3 and for aldehydes and ketones
o25 mg m3.
The experimental set-up contained totally six
chambers, three with UVA-light (black light) and
three with normal office light (see Figs. 2 and 3). In
the UVA-chamber the light intensity on the surface
of the painted system was 1–2 W m2 and it
comprised only UVA light. In the reference
chamber the UVA light intensity was 5–10 mW m2
and the total light intensity was 600–800 lx.
Fig. 2. A sketch of the experimental set-up.
2.3.1. Measurement procedures
2.3.1.1. Emissions from paints. A fresh paint ap-
plied onto glass was placed into the chamber and let
dry for 48 h, then the UVA-light was switched on.
Air samples were collected into DNPH-cartridges
using a pump (FLEC Air Pump 1001) with an
airflow rate of 200 ml min1. Duplicate samples
were collected after 1 day (6 l), 7 days (6 l) and 14
days (6 l) radiation.
2.3.1.2. Formaldehyde tests. A fresh or aged paint
applied onto glass (all paints) or plaster (paints A
and B) was placed into the chamber 48 h prior to
start of the sample collection. A total of
1500 mg m3 formaldehyde was injected through a
septum into the environmental chamber. After
injection the chamber was let to stabilize for
2 min, before the UVA-light was switched on.
Duplicate samples were collected into DNPH-
cartridges after 15 min (0.4 l, 200 ml min1), 2 h
(2 l, 200 ml min1) and 24 h (6 l, 200 ml min1).
2.3.1.3. VOC-mixture tests. A fresh or aged paint
applied onto glass (all paints) or plaster (paints A
and B) was placed into the chamber 48 h prior to
 ARTICLE IN PRESS
J. Auvinen, L. Wirtanen / Atmospheric Environment 42 (2008) 4101–4112
Fig. 3. An office light (reference) environmental test chamber (left) and UVA-light test chamber (right).
start of the sample collection. A mixture of five
different VOCs (n-heptane, toluene, a-pinene, 1-
hexanol and nonanal) was injected into the chamber
using a syringe. The concentration of each indivi-
dual VOC was approximately 600 mg m3, and the
total injected VOC amount was 3000 mg m3. Air
samples were collected into TENAX TA and
DNPH-cartridges successively. Duplicate air sam-
ples were collected after 15 min (0.2 l, 200 ml min1),
2 h (0.4 l, 200 ml min1) and 24 h (1 l, 200 ml min1).
Thus, both VOCs and their decomposition pro-
ducts, such as ketones and aldehydes, were collected
simultaneously.
2.3.2. Analysis of aldehydes and ketones
Carbonyl compounds were collected and analyzed
according to ISO 16000-3 (2001). After sampling, the
ends of the cartridges were capped and put into
pouches. The samples were stored in a refrigerator
(maximum for 14 days) before the analysis was
carried out. The analytes were eluted from the
cartridge with 5 ml of acetonitrile. The separation
was carried out in a C18 analytical column and the
quantification was performed with a UV detector at
the wavelength of 360 nm. The mixture of seven
DNPH derivatives of aldehydes and ketones (Carb-
Carbonyl-DNPH Mix 1 Supelco) was used for
calibration and quantification. The day-to-day varia-
tion of the components was 1.6–4.3% (n ¼ 28) at a
concentration range of 0.5–0.9 mg ml1. The limit of
detection for the total amount of carbonyl com-
pounds is indicated in Tables 2 and 3.
2.3.3. VOC-sample analysis
Sealed glass jars containing the collected VOC-
samples were stored in a refrigerator for a maximum
4105
of 8 days prior to sample analysis. The analysis was
performed by the GC/MS-method according to ISO
16000-6 (2004). The accuracy of the analysis is
15–41% depending on the compound, being 25%
on average. The limit of detection is also compound
dependent being 10 ng sample1 on average, thus
being 1 mg m3 for a 10 l sample. The analysis results
were given as concentrations of VOCs in sampled
air expressed as mg m3.
3. Results and discussion
3.1. Photocatalytic degradation of paints
When photocatalytic degradation occurs, organic
compounds such as formaldehyde, acetaldehyde,
and acetone, may be formed. These compounds
may even remain stabile (Hodgson et al., 2007). In
this part of the study the source of compounds
detected is mainly the paint, because the incoming
air was clean of impurities and the chambers’ blank
values were negligible.
Measured values of formaldehyde are clearly
higher in the UVA-chamber than in the reference
chamber. Also the photocatalytic paint E produces
more formaldehyde than the photocatalytic paint F
and the reference paint (Fig. 4). Paint E also
produces higher amounts of other aldehydes and
ketones (acetaldehyde, acetone, propianalaldehyde,
etc.) than the other two paints.
The binder of paint E is a PVAc–ethene
copolymer and the binder of paint F is a styrene–
acrylate copolymer. The binder of the reference,
non-photoactive, paint is PVAc. The concentration
of formaldehyde exceeded the recommended Fin-
nish limits for indoor air, which is 100 mg m3 for
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4106 J. Auvinen, L. Wirtanen / Atmospheric Environment 42 (2008) 4101–4112

Table 2
Detected carbonyls in the formaldehyde experiment for aged paints

Paint UVA-light aged paint (mg m3) Normal light aged paint (mg m3)

15 mina 2 hb 24 hc 15 mina 2 hb 24 hc

Photocatalytic paint Ad
Formaldehyde 201 610 371 182 114 186
Acetaldehyde 1358 4084 2725 300 286 280
Acetone 1152 1158 1145 598 170 105
Photocatalytic paint Bd
Formaldehyde 752 1065 295 374 444 387
Acetaldehyde 2585 6155 753 692 898 781
Acetone 441 2363 346 63 145 191
Photocatalytic paint Cd
Formaldehyde 712 554 37 438 391 125
Acetaldehyde 946 1538 186 440 313 167
Acetone 3534 737 163 63 88 118
Photocatalytic paint Dd
Formaldehyde 583 696 233 556 387 177
Acetaldehyde 790 820 300 175 145 144
Acetone 925 3800 2409 125 423 755
Photocatalytic paint E
Formaldehyde 230 257 228 312 199 107
Acetaldehyde 51 274 250 oD.L. 19 57
Acetone oD.L. 34 29 67 47 14
Photocatalytic paint F
Formaldehyde 390 219 54 381 223 59
Acetaldehyde oD.L. 23 48 27 15 15
Acetone 100 33 15 oD.L. oD.L. 16
Reference paint
Formaldehyde 511 298 39 612 285 38
Acetaldehyde oD.L. 35 oD.L. oD.L. oD.L. oD.L.
Acetone oD.L. oD.L. 12 oD.L. oD.L. oD.L.
a
Detection limit for 15 min ¼ 50 mg m3.
b
Detection limit for 2 h ¼ 20 mg m3.
c
Detection limit for 24 h ¼ 10 mg m3.
d
Also noteworthy concentrations of propionaldehyde, butylaldehyde and benzaldehyde were detected. oD.L. ¼ below detection limit.

indoor climate category S3 (Classification of Indoor
Climate, 2000). This is also the limit stated by health
authorities.
3.2. Photocatalytic removal of formaldehyde
The decomposition of formaldehyde by
active radicals dOH and dO
2 (hydroxyl and
oxide) follows the chain reaction resulting
formation of water and carbon dioxide
(2)–(4)) (Ao et al., 2004; Avery, 2006):
HCHO þ OHd ! HCOd þ H2 O
HCOd þ OHd ! HCOOH
HCOOH þ 2hþ ! CO2 þ 2Hþ (4)
3.2.1. Effect of the substrate
Three different substrates were investigated to
understand the effect of the substrate on photo-
catalytic reactions. Fig. 5 shows that the substrate
highly does not have any noteworthy effect on photo-
catalytic reactions, i.e. the graphs are almost
super-
in the identical independent of the substrate. It is also
(Eqs. very difficult to observe the degradation of for-
maldehyde injected into the chamber with time,
since the formaldehyde concentration increases
(2) dramatically under UVA-light. The injected for-
maldehyde concentration reaches zero in the empty
(3) chamber in 24 h.
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J. Auvinen, L. Wirtanen / Atmospheric Environment 42 (2008) 4101–4112 4107

Table 3
Detected carbonyls in VOC-experiment for aged paints

Paint UVA-light aged paint (mg m3) Normal light aged paint (mg m3)

15 mina 2 hb 24 hc 15 mina 2 hb 24 hc

Photocatalytic paint Ad
Formaldehyde 111 279 780 122 46 317
Acetaldehyde 160 2068 3380 175 105 580
Acetone 463 248 1010 2887 238 292
Photocatalytic paint Bd
Formaldehyde 271 707 1155 231 158 728
Acetaldehyde 384 3802 3223 174 278 1506
Acetone 817 230 714 oD.L. 638 108
Photocatalytic paint C
Formaldehyde 285 399 51 178 58 127
Acetaldehyde oD.L. 241 132 oD.L. 76 90
Acetone 1544 oD.L. 75 1361 oD.L. 286
Photocatalytic paint Dd
Formaldehyde 176 371 464 218 101 332
Acetaldehyde 141 272 681 75 97 291
Acetone oD.L. 101 2556 oD.L. 48 606
Photocatalytic paint E
Formaldehyde 178 150 462 136 54 137
Acetaldehyde oD.L. 167 563 122 34 169
Acetone oD.L. oD.L. 71 oD.L. oD.L. 22
Photocatalytic paint F
Formaldehyde 145 267 oD.L. 58 58 48
Acetaldehyde oD.L. 135 oD.L. 298 91 159
Acetone oD.L. 48 75 oD.L. oD.L. oD.L.
Reference paint
Formaldehyde 111 67 36 52 57 28
Acetaldehyde oD.L. oD.L. oD.L. oD.L. oD.L. oD.L
Acetone oD.L. 142 58 oD.L. oD.L. 38
a
Detection limit for 15 min ¼ 50 mg m3.
b
Detection limit for 2 h ¼ 20 mg m3.
c
Detection limit for 24 h ¼ 10 mg m3.
d
Also noteworthy concentrations of propionaldehyde, butylaldehyde and benzaldehyde were detected. oD.L. ¼ below detection limit.

Degradation of organic binder, UVA-chamber Degradation of organic binder, normal chamber

300 300
Formaldehyde (µg/m3)
Formaldehyde (µg/m3)

250 250
200 200
150 150
100 100
50 50
0 0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Time (d) Time (d)

Paint A Paint B Reference Paint

Fig. 4. Formaldehyde emissions from different photocatalytic paints and from the reference paint.
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4108 J. Auvinen, L. Wirtanen / Atmospheric Environment 42 (2008) 4101–4112

Photocatalytic Paint A on different subtrates Photocatalytic Paint A on different substrates

(UVA-light) (normal light)
1800 1800
Formaldehyde (µg/m3)

Formaldehyde (µg/m3)
1600 1600
1400 1400
1200 1200
1000 1000
800 800
600 600
400 400
200 200
0 0
0 4 8 12 16 20 24 -4 0 4 8 12 16 20 24
Time (h) Time (h)

Paint A / Gypsum Paint A / Glass

Paint/ Polymeric Empty Chamber

Plaster

Fig. 5. Photocatalytic degradation of formaldehyde on different substrates with paint A (fresh paint). Left is the UVA-chamber and right
is the reference chamber.

Formaldehyde concentrations, aged paint Formaldehyde concentrations, aged paint

(UVA-light) (normal light)
1600 1600
Formaldehyde (µg/m3)

Formaldehyde (µg/m3)

1400 1400
1200 1200
1000 1000
800 800
600 600
400 400
200 200
0 0
0 4 8 12 16 20 24 0 4 8 12 16 20 24
Time (h) Time (h)

Paint A Paint C Paint E Reference Paint

Paint B Paint D Paint F

Fig. 6. Formaldehyde concentrations for paints of different ages applied onto glass under UVA (left) and normal light (right).

3.2.2. Photocatalytic degradation of formaldehyde The concentration of different aldehydes and

In Fig. 6 is presented the formaldehyde concen- ketones were much higher and their formation
trations of aged paint systems applied onto glass much faster in the UVA-chamber than in the
under different lighting conditions. The amount of reference chamber (Table 2). Also the amounts
detected formaldehyde varies clearly between UVA were clearly higher for some paints, but the
and normal light. The injected concentration amounts tended to decrease with time (Fig. 7, left).
(1500 mg m3) decreases first (15 min) under UVA- On the other hand in a reference chamber not
light. Then the formaldehyde concentration in- only the amounts were less, in some paints, A
creases for paints A, B and D. From paints A, B, and D, the level of pollutants was still increasing
D and E concentrations after 24 h testing period are (Fig. 7, right). The aged paints were generating
significantly higher compared to those of the indoor pollutants more than even the fresh ones
reference paint under both UVA and normal light. (Table 2).
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J. Auvinen, L. Wirtanen / Atmospheric Environment 42 (2008) 4101–4112 4109

Aldehydes and ketones, aged paint Aldehydes and ketones, aged paint
(UVA-light) (normal light)
2000

Aldehydes and ketones

Aldehydes and ketones

12000 1800
1600
10000 1400

(µg/m3)
8000 1200
(µg/m3)

1000
6000 800
4000 600
400
2000
200
0 0
0 4 8 12 16 20 24 0 4 8 12 16 20 24
Time (h) Time (h)

Paint A Paint C Paint E Reference Paint

Paint B Paint D Paint F

Fig. 7. The total sums of aldehydes and ketones detected in a formaldehyde-chamber test for aged paints applied onto glass under UVA
(left) and normal light (right).

VOC degradation, aged paint

VOC degradation, aged paint
(UVA-light)
(normal light)
3000 3000

2500 2500
TVOC (µg/m3)
TVOC (µg/m3)

2000 2000

1500 1500
1000 1000
500 500
0 0
0 4 8 12 16 20 24 0 4 8 12 16 20 24
Time (h) Time (h)

Paint A Paint C Paint E Reference Paint

Paint B Paint D Paint F

Fig. 8. Decrease/degradation of the VOC-mixture for the aged paints in UVA (left) and reference chamber (right).

3.3. Photocatalytic removal of VOCs paints: A, B, C, and D. These paints were able to
decompose the injected pollutants faster than the
The removal and degradation of VOCs is other paints. However, the degradation effect
commonly investigated on different TiO2 surfaces. concerned only two of the injected pollutants. These
The results are quite promising, but the information two tracer compounds were 1-hexanol and nonanal,
on how TiO2 works in paint is quite scanty. The which are the most reactive ones from the mixture
mixture of five different indoor VOCs was injected because of their functional groups.
into the chamber and the concentrations were The VOC-concentrations were different in differ-
observed. Fig. 8 shows the decomposition, removal ent lighting conditions. This is valid especially for
or degradation of VOCs compared to a normal non- paint A (Figs. 8 and 9). The results were also
photoactive paint. The measured concentrations different between new and aged paints. One reason
from the photoactive paints did not markedly differ for this is that VOC-containing, film-forming agents
from that of the reference paint. The removal of and additives evaporate from the fresh paint film
VOCs can be explained with adsorption onto during testing and should have already evaporated
different surfaces, photocatalytic effect and air from the aged ones prior to testing. The lowest
exchange rate (Uhde and Salthammer, 2007). A values were achieved with the aged paint C (lime
clear photocatalytic effect was observed for four paint). In addition to VOC-concentrations, the
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4110 J. Auvinen, L. Wirtanen / Atmospheric Environment 42 (2008) 4101–4112

VOC degradation, fresh paint VOC degradation, fresh paint

(UVA-light) 3000 (normal light)
3000 2500
2500

TVOC (µg/m3)
2000
TVOC (µg/m3)

2000
1500
1500
1000
1000
500 500

0 0
0 4 8 12 16 20 24 0 4 8 12 16 20 24
Time (h) Time (h)

Paint A Paint C Paint E Empty Chamber

Paint B Paint D Reference Paint

Fig. 9. Decrease/degradation of the VOC-mixture for the fresh paints in UVA (left) and reference chamber (right).

Aldehydes and ketones, aged paint Aldehydes and ketones, aged paint
(UVA-light) (normal light)
6000
Aldehydes and ketones
Aldehydes and ketones

6000 5000
5000
4000
(µg/m3)

4000
(µg/m3)

3000
3000
2000 2000
1000 1000
0 0
0 4 8 12 16 20 24 0 4 8 12 16 20 24
Time (h) Time (h)

Paint A Paint C Paint E Reference Paint

Paint B Paint D Paint F

Fig. 10. The total sums of aldehydes and ketones detected in a VOC degradation-chamber test with aged paints applied onto the glass
plate in UVA (left) and reference chamber (right).

aldehyde and ketone concentrations were also photocatalysis. This self-degrading effect may result
measured simultaneously (Fig. 10, Table 3). The in relatively high quantities of organic compounds,
same kinds of results were obtained as in Fig. 6, like aldehydes and ketones. These compounds are
photocatalytically active paints generated relatively quite stabile indoor air pollutants and may decrease
high concentrations of aldehydes. Some paints (A, the quality of the air (Zhang et al., 1994). To
B, and D) were still generating relatively high prohibit this kind of unwanted behaviour, the
concentrations of aldehydes and ketones after binder should be stabile enough to endure highly
24 h. Measured temporary concentrations were as active radicals.
high as 1000–6000 mg m3, which clearly (10–60 In dynamic conditions, the removal of formalde-
times) exceeds normal indoor concentrations. These hyde was not detected. On the other hand, some
results indicate both the degradation of VOCs and paints even increased the formaldehyde concentra-
the degradation of the paint itself. tion. In addition to formaldehyde great amounts of
other aldehydes and ketones were also formed. The
4. Conclusions test results also indicate that the detected amounts
of side products were higher under UVA-light than
The organic material of paints and coatings, such under normal light. The aged photocatalytic sur-
as binders and additives, can be decomposed due to faces gave results similar to those of the fresh ones,
 ARTICLE IN PRESS
J. Auvinen, L. Wirtanen / Atmospheric Environment 42 (2008) 4101–4112
although the concentrations were slightly higher for
some aged paints. One reason for this could be that
the chemical nature of the paint film has changed
due to ageing. Some additives have vanished due to
evaporation and photocatalysis, and this results in a
higher activity of the TiO2. Thus, the TiO2 may
react more efficiently with airborne compounds and
its active surface area has also increased. The
different substrates (glass, gypsum or polymeric
plaster) did not have a noteworthy influence on the
photocatalytic behaviour of the paints.
The VOC investigations showed results similar to
those noted with formaldehyde, as far as less-active
paints are concerned, i.e. the compounds introduced
into the chamber were not decomposed. Photo-
catalytically active paints were able to decompose
only more reactive VOCs (1-hexanol and nonanal),
but at the same time they also generated, for
instance, formaldehyde, acetaldehyde, and acetone.
All perhaps, generated compounds could not be
collected or analysed in this research project.
However, these measurements already show that
photocatalytic reactions do not generate only
carbon dioxide and water. In addition to that, the
generated concentration levels of the reaction
products may cause adverse health effects in people
(WHO, 1989).
Proper functioning of photocatalytic coatings still
needs constant development. The future will show if
it is possible to develop photocatalytic coatings
which can mineralize indoor air contaminants. The
potential of photocatalytic coatings has already
shown some capacity for outdoor applications
(reduction of NOx) (Salthammer and Fuhrmann,
2007).
Acknowledgments
Thanks to VTT Technical Research Center of
Finland for the VOC-analysis. Special thanks to
Prof. Vesa Penttala, Helsinki University of Tech-
nology, Laboratory of Buildings Materials Tech-
nology, for his advice and supplying laboratory
facilities. The project was financially supported by
Tikkurila Oy, for which we want to express our
gratitude.
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