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Environment International 33 (2007) 694 – 705 www.elsevier.

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Review article

Volatile organic compounds in indoor environment and photocatalytic oxidation: State of the art
Shaobin Wang ⁎, H.M. Ang, Moses O. Tade
Department of Chemical Engineering, Curtin University of Technology, GPO Box U1987, Perth, WA 6845, Australia Received 26 November 2006; accepted 14 February 2007 Available online 26 March 2007

Abstract Volatile organic compounds (VOCs) are the major pollutants in indoor air, which significantly impact indoor air quality and thus influencing human health. A long-term exposure to VOCs will be detrimental to human health causing sick building syndrome (SBS). Photocatalytic oxidation of VOCs is a cost-effective technology for VOCs removal compared with adsorption, biofiltration, or thermal catalysis. In this paper, we review the current exposure level of VOCs in various indoor environment and state of the art technology for photocatalytic oxidation of VOCs from indoor air. The concentrations and emission rates of commonly occurring VOCs in indoor air are presented. The effective catalyst systems, under UV and visible light, are discussed and the kinetics of photocatalytic oxidation is also presented. © 2007 Elsevier Ltd. All rights reserved.
Keywords: Photocatalytic oxidation; Volatile organic compounds; Indoor air; UV–vis light

Contents Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VOCs exposure in indoor environment . . . . . . . . . . . . . . . . . Photocatalysts and photocatalytic oxidation . . . . . . . . . . . . . . . 3.1. UV-light irradiated catalysts . . . . . . . . . . . . . . . . . . . 3.2. Visible-light irradiated catalysts for VOCs . . . . . . . . . . . . 4. Effect of water vapour and other gaseous compounds on photocatalytic 5. Reaction mechanism and kinetics . . . . . . . . . . . . . . . . . . . . 6. Summary and perspectives . . . . . . . . . . . . . . . . . . . . . . . Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1. 2. 3. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 694 695 697 697 700 702 702 704 704 704

1. Introduction Indoor air quality (IAQ) has become an important community concern due to the increased amount of personal time spent in indoor environment. Nowadays, people generally spend more
⁎ Corresponding author. E-mail address: wangshao@vesta.curtin.edu.au (S. Wang). 0160-4120/$ - see front matter © 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.envint.2007.02.011

than 80% of their time in an indoor environment such as home, office, car and shopping centre. Some studies showed that the level of pollutants in indoor environment is actually higher than that in outdoor environment. Indoor air pollutants mainly include nitrogen oxides (NOx), carbon oxides (CO and CO2), volatile organic compounds (VOCs), and particulates. VOCs are well-known indoor pollutants. These pollutants are emitted from different sources such as combustion by-products, cooking,

These VOCs have a close relation with the sick building syndrome (SBS). 7–9. 1997. thermally catalytic oxidation is not economically feasible at low pollutant concentrations. 4. vehicles. offices. Recently. VOCs exposure in indoor environment Indoor air was defined as the air in non-industrial areas of dwellings. 2. The concentrations of VOCs are dependent on the environment. 4. 2. . 2004. 7. 7 2. 11 1. 3. Roark et al. 12: office equipment. etc. 11 9 1. 2004) are promising technologies for air purification because the pollutants can be oxidised to H2O and CO2. In the past two decades. 2004) and photocatalytic oxidation (PCO) (Zhao and Yang. Since the 1970s. mutagenic. / Environment International 33 (2007) 694–705 695 construction materials. In general. schools. aldehydes. and air cleaning. increase ventilation. and consumer products. because the semiconductor catalysts are inexpensive and capable of mineralising most organic compounds effectively. a lot of investigations have been conducted in photocatalytic oxidation of gaseous VOCs and several types of photocatalyst systems have been developed (Hoffmann et al. 1994). namely source control. Thus it is necessary to investigate the catalytic performance of catalysts at low pollutant level. Table 1 lists the classes of VOCs identified in indoor air. 9–11 1–7. However. and halocarbons are the most occurring compounds. 7–10 1–9. In general. 3: school. this technique is still in the developmental stage for VOCs removal from indoor air. 12 1–12 1–4. 7–9 1. a lot of investigations have been carried out for measurement of the indoor air concentrations of VOCs all around the world (Brown et al. However. Furthermore. 7. 8: solid woods.. The mean concentration of each VOC in established buildings is generally below 50 μg/m3. 2: new and renovated buildings. 7: wood-based panel and furniture. Traditional pollution control method such as adsorption by activated carbon merely transfers pollutants from gaseous phase to solid phase. which is one of many terms used by occupants to describe symptoms of reduced comfort or health. 7. While concentrations in the ppm range are typical for chemical stream concentration. Indoor sources vary tremendously depending on the nature of the facility and are too diverse for any simple classification. 2. 9 1–4. Wang et al. The future research directions will also be presented. However. The important factors that influence the catalytic activity and the kinetics will be discussed. With the increasing concerns on the indoor air quality. 9. in which aromatics. trains. The emission of volatile organic compounds from building materials has been recognised as the largest source of indoor air pollutants. three methods are suggested to improve the indoor air quality. air quality in cars and aircraft cabins has also raised much concern. sub-ppm levels or parts per billion (ppb) concentrations are commonly associated with indoor (buildings. Increased ventilation might even transport more pollutants from the outdoor environment.. The mean concentrations of VOCs and total VOCs in established buildings are generally greater than those established public buildings and VOC concentrations in new buildings are much greater than those in established buildings (Brown et al.. 1997). 4. 1995). Thus. The exposure level of VOCs in indoor environment is also significantly dependent on the sources and emission rates. 5. 11 1: Established buildings. Source control is often ungovernable and unavoidable in the metropolis. Carp et al. 11 1–4. thermally catalytic oxidation requires high temperatures of 200–1200 °C for efficient operation and hence expensive. 11. Extrapolation of the oxidation data collected at concentrations much higher than the intended application may not be valid (Obee and Brown. we will present updated progress in this area. Advanced oxidation processes (AOP) such as thermal oxidation destruction (Drysys. 2003).S. 2. but higher than 5 μg/m3. Table 2 lists some specific indoor sources Table 1 Classes of VOCs and their possible emission sources (Cheng and Brown. 10: cleaning products. most investigations concentrated on the VOC destruction at higher concentrations of the parts per million (ppm) levels. 6: floor coverings. air cleaning remains to be the most feasible option to improve the indoor air quality. 2. office equipment. 2003. Everaert and Baeyens. and hospitals. planes. 6–12 11 2. According to the definition of the World Health Organisation (WHO). Several investigations have found that different inlet contaminant concentrations lead to different reaction rates (Zhao and Yang. 5: carpets. In this review. 11: unflued gas heaters and electric ovens. 4: new car interiors. 1994). 7. more researches have focused on photocatalytic oxidation of VOCs at ppb level in recent years. or teratogenic (Alberici and Jardim. We will discuss the VOC exposure level at various indoor environments and summarise various catalyst systems for photocatalysis under UV and visible light.) VOCs. and excluding pesticides. However. reaction rate is enhanced with the increasing of inlet concentration of pollutants. 9: paints. 1995). 2003) VOC class Aliphatic and cyclic hydrocarbons Aromatic hydrocarbons Aldehydes Terpenes Alcohols Esters Halocarbons Glycols/glycolethers/glycolesters Ketones Siloxanes Alkene Organic acids Ethers Other VOCs Environment and sources 1. It is found that indoor air typically contains a greater number of VOCs at higher concentrations than outdoor air. there are limited studies on the photodegradation of VOC pollutants at typical indoor levels. VOCs are referred as all organic compounds in the boiling point range of 50–260 °C. Photodegradation usually occurs at room temperature and pressure for air purification and may be more cost-effective than other conventional techniques such as activated carbon adsorption and chemical scrubbers. contributions from outdoor air can be an important component through leakages and makeup air in ventilation systems. In some cases. Many VOCs are known to be toxic and considered to be carcinogenic. because these vehicles are also typical indoor environments. There is a variety of sources of VOCs in indoor air...

1992) Compound Paradichlorobenzene Methylene chloride Formaldehyde Styrene Acetaldehyde Acrolein Toluene diisocyanate Phthalic acid anhydride Trimellitic acid Triethylene tetraamine Benzyl chloride Benzyl chloride Ethylene oxide Amines (cyclohexyloamine. gasoline.. perfumes Wood preservative agent Wood preservative formulations of organic vapours (Namiesnik et al. total VOCs are much higher. undecane) Terpenes (limoneme. 1994). fabric softeners. fabrics. cosmetics Plastics. disinfectants. adhesives. public buildings. maximum and minimum values were quite similar across all transportation modes (Nagda and Rector. window cleaners. fuels. lacquers. office. woodburning. adhesives. Wang et al. A comparison of cabin air quality (CAQ) is shown in Table 4. 1992) and Table 3 shows the total VOC emission rates in indoor sources (Brown et al. 2003). adhesives Resins. toluene. ceiling tiles Combustion products (smoking. deodorants. . it is seen that the construction coverings and household cleaning products make the significant contribution to the air pollutants in indoor environment. Compared with indoor air quality in various buildings. fabric protectors Industrial strength cleaners Paints. and mobile cabins are much similar. From the tables. 2003).1-trichloroethane Carbon tetrachloride Aromatic hydrocarbons (toluene. trimethylbenzenes) Aliphatic hydrocarbons (octane. cigarettes. by-product of the combustions of wood. plastics.1. In general. a commonly used solvent for coatings and adhesives. The most occurring VOCs in indoor environment include ethanol. textiles. aircraft. however. mold growth on leathers Component of oak-wood. paints. lacquers solvents. and subway is also important. The reported maximum VOC levels are comparable across the different transportation modes. PCB-containing fluorescent light ballasts. foam Insulation. varnishes. gasoline. The higher levels of m-/p-xylenes found in buses and subways relative to aircraft are consistent with the presence of gasoline as the primary fuel for these vehicles. combustion sources Paints. dishes) Wearing or storing dry-cleaned clothes. aerosols Epoxy resins } } Vinyl tiles plasticized with butyl benzyl phthalate Sterilizers (hospitals) Volatilized with the steam boiler systems (corrosion inhibitors of steam pipes and other equipment) Putrefactive degradation of casein-containing building materials Smoking Wearing or storing dry-cleaned clothes Chlorinated water (showering. aromatics.. kerosene and cotton Polyurethane foam. aldehydes. In summary. morpholine) Volatile amines Benzene Tetrachloroethylene Chloroform 1. paints. cosmetics and adhesives Lacquers. decane. / Environment International 33 (2007) 694–705 Table 2 Specific indoor sources of organic vapours (Namiesnik et al. a variety of VOCs including alcohols. vinyl chloride Alcohols Ketones Ethers Esters Pentachlorophenol Lindane Source material(s) Moth crystals. xylenes. diethylaminoethanol. varnishes. acetone. and methylene chloride. soaps. solvent usage Pressed wood products. ethylbenzene. aerosols sprays. washing clothes. limonene. room deodorants Paint removers. The individual VOC is usually lower than 50 μg/ m3. measured air pollutant concentrations in aircraft cabins are comparable with those reported for residential and office buildings. The VOCs concentrations in indoor environments such as home. paint thinners. epichlorohydin. plasticizers. and halocarbons will occur in indoor environment. bus. food beverages Household insecticides Termicide Termicide Transformers. polish removers. paints Glues. flavors. dyes. combustion products Scented deodorizers. preventives. polishes. The building materials and coverings are the major contributors to indoor VOCs with various emission rates. kerosene heaters) Incinerator stack emission Contamination of pentachlorophenol used as wood preservative Monomers may escape from polymers Aerosols. A comparison of CAQ with that observed in residential and office buildings is also given in Table 5 (Nagda and Rector. heptachlor Diazinon PCBs PAHs Polychlorinated dibenzofurans (PCDs) Polychlorinated dibenzo-p-dioxins (PCDDs) Acrylic acid esters. For 2-butanone (methyl ethyl ketone).696 S. air quality in mobile cabin including train. resins. with acetone and ethanol being higher in aircraft cabin air. as well as the external influence of other ground-based transportation vehicles found in urban areas. α-pinene) Chloropyrifos (Dursban) Chlordane.

Polyurethane lacquer 7. Polyurethane foam 12.9 Acetone 21. and the charge will transfer between electron–hole pairs and adsorbed species (reactants) on the semiconductor surface.9 121. Felt-carpet 9.0–8. Water-based adhesives 3. Furniture spray polish 9. Water-based waxes/detergents 8.7 × 104 2. the requirement wavelength of light excitation for TiO2 is 388 nm. 2 presents the band gap of several semiconductors.2–5. then photooxidation happens.0 × 106–9.3–61. a commercially available Degussa P25 TiO2. 1 presents the diagram of photocatalytic oxidation. Sealant (including silicones) 5.8–2.6 (dichloromethane) Naphthalene 0–1.1 × 106 1.2 eV.1.3 × 103 1.9–5. Fe2O3.0–167. TiO2 is the most important and widely used catalyst.5 7–54 15–39 13–27 m/p-Xylenes 2.6 1. an important step of photoreaction is the formation of hole–electron pairs which need energy to overcome the band gap between the valence band (VB) and conduction band (CB). CdS.1 Tetrachloroethylene 32–13 Toluene 4.6 × 105–2. Floor wax paste 11.2 × 105–1.8 40. Floor cleaners 10. Floor varnishes (3 types) 8. Textile floor covering 6. 1994) Source description Household products (“wet”) 1.6–68 2.1 × 106 2. Painted gypsumboard/particleboard 10.S.2 × 106 3. Rubber-backed nylon carpet 8. for the photocatalytic reaction.3 × 104 120–2.4–12. Other semiconductors such as ZnO.5–92. Liquid cleaner/disinfectant 6.5–10.. excellent stability.8–58.4 × 103 30–103 80–1.7 2.9 × 104–4.7–58 4.7 × 106 1.6 × 103 220–590 300 50–180 80–10 240–260 120–140 120 30–300 30 20 10 Table 5 Comparison of cabin air quality with building air quality (μg/m3) Chemical Acetaldehyde Acetone Benzene 2-Butanone Ethanol Formaldehyde n-Hexane Limonene Methylene chloride (dichloromethane) Naphthalene 2-propanol (isopropyl alcohol) Propionaldehyde Tetrachloroethylene Toluene m/p-Xylenes o-Xylene Aircraft 10.0 2. UV-light irradiated catalysts At the early stage of photocatalyst development.0 × 106 1.0 × 105 b 104–1. and low cost.7 × 10 b104–2.5 17–9. the pairs of electron–holes are created in the semiconductor. Waxes spread on surface 3.7–9. Wang et al.2 2.0 × 104 2. Carpet spray cleaner 7.1 6.9 0–6. has been used as a standard photocatalyst for oxidation of gaseous or aqueous pollutants under UV or near-UV light.6 30.8 2-propanol (isopropyl alcohol) 12–92.7–12 11–66 4.2 × 104 1. these are not as popular as TiO2. which can be reduced and oxidised by a photonic activation through an efficient abTable 3 Total VOC emission rates of indoors sources (Brown et al.9 1–17 190–490 1–6 Methylene chloride 3. Other semiconductors are also employed.5 n-Hexane 0–3 2–6 0–6 Limonene 4. which is in the ultraviolet range. Plastic floor covering 7.1 3.0 1.7 × 104 6 × 103 830–4.7 × 105 300–7.7 0–33 7–63 9–23 Propionaldehyde 1. A good photocatalyst is characterised by its capability to adsorb simultaneously two reactants.4–17.1–121. Floor wax 13.0 4.4 × 107 1.4 × 103 410 300–2.4–45.3 2–4 2–6 4–7 2-Butanone 3. Wood stain 6. Particleboard 11. Solvent-based adhesives 2. Toilet deodorizers 4. Mineral wool 1.1 × 10 –1. 3. Liquid floor detergent Construction product (“wet”) 1.5 × 105 6. New vinyl flooring 2. For the photocatalytic oxidation.7 Residential 32–130 8–34 120–490 21–450 Office 6.5–5.6–37 3.7 } } sorption (hγ N Eg). however. Most of the investigations for indoor air photocatalytic oxidation used this catalyst. Currently.8 18.5–5.5 7–65 37–320 18–120 6–25 .7 49–92 30–73 30–92 Benzene 0–7. Photocatalysts and photocatalytic oxidation Fig.4 × 103 40 1. Wallpapers (including vinyl) 13. When the energy provided (photon) is larger than the band gap.7–14 5.7–16.1 × 106 1. Gypsumboard 14.7–86.4–61.7 × 104 Table 4 Reported air quality in different modes of public transportation (μg/m3) Chemical Aircraft Train Bus Subway Acetaldehyde 4.7 × 103 2. Based on the value of band gap of 3. GRP sheeting 15.3 × 106–3.0–12.5 3–9 6–48 5–50 o-Xylene 0–2.6 × 108 1. Rubber floor covering 3.0 × 104 1. / Environment International 33 (2007) 694–705 697 3. Plywoods 4. ZnS. Room deodorizers 5. Due to a variety of VOCs occurring in 5.7–10 3. Fig. Wall/flooring glue (EVA) 4. Dry-cleaned clothing 12.1–22 2. due to its high photoactivity.0 324–1116 5. Polystyrene foam Emission rate (μg/m2/h) Up to 2. Solvent-based waxes/detergents 2.1 × 103 6 7 5. SnO2 are also commonly used catalysts. PVA glue (water-based) Construction products (“dry”) 1.9 3–11 4–18 4–17 Ethanol 154–3625 170–1700 50–260 130–300 Formaldehyde 1.8–12 6.

Later Obee reported the investigation of photooxidation of toluene and formaldehyde using another type of reactor. three types of films were prepared by a dip-coating process for the photocatalysed decomposition of 1-butene at a low concentration of 2. (c) reduction of acceptor (A).. acetaldehyde. they used the Degussa P25 TiO2 as catalyst and focused the study on the effects of humidity on the oxidation rates of formaldehyde. The surface reaction is the rate-limiting step. Research results concerning the photocatalytic activity and selectivity of benzene using P25 TiO2 and illuminated by a fluorescent black light was then presented by Jacoby et al. For other VOCs. Band positions (top of valence band and bottom of conduction band) of several semiconductors together with some selected redox potentials (Carp et al. 2. The nanoscale TiO2 samples were found to be highly active for the photodegradation of toluene. 1998). 2004). Obee and Brown first reported an investigation of photocatalytic oxidation of VOCs using TiO2 for indoor air. toluene. performing the reaction at room temperature resulted in rapid deactivation of TiO2 catalysts due to the chemisorption of intermediates. Under the experimental conditions. Then they used the nanoscale TiO2 catalysts for the photocatalytic oxidation of toluene (Cao et al. 1996) and compared the results of two reactor designs. and o-. toluene and xylenes in indoor air (Pichat et al. The average concentrations of benzene. Wang et al. A design model was developed which could be used for two reactors. Stevens et al. Quantum size effects were mainly responsible for the high photoactivity achieved by SnO2. reported on an examination of the operational characteristics of four PCO reactor designs using P25 TiO2 for the oxidation of VOCs. the PCO destruction efficiencies were Fig. m-. (2002) evaluated the application of P25 TiO2 photocatalysis for the removal of five target VOCs. In their study. ethyl benzene. Table 6 summarised the results on various photocatalytic oxidation for indoor VOCs. . such as benzaldehyde and benzoic acid. (1996). toluene and xylenes were indeed reduced by a factor of 2–3 in an ordinary nonairtight room (Fig. However. In the investigation.. the nanoscale photocatalysts showed higher photoactivity than P25 TiO2 (Cao et al. The dependencies of humidity and contaminant concentrations on the oxidation rates are explained as being the results of competitive adsorption on available hydroxyl adsorption sites and of changes in hydroxyl radical population levels (Obee and Brown. under otherwise identical conditions. and 1. in the laboratory photoreactor without photoexcitation of O3.3-butadiene. Assisted by adding hydrochloric acid. Under UV illumination. 2004). p-xylenes in-vehicle air. respectively (Carp et al. photocatalysis is also effective. Based on the work. / Environment International 33 (2007) 694–705 Fig. PCO of the formaldehyde and acetone was nearly 100% for all reactor designs (Stevens et al. 2000). Jo et al.698 S. (1999b) investigated the different catalytic activities of SnO2 and Degussa P25 TiO2. Main processes occurring on a semiconductor particle: (a) electron–hole generation. 1. An important finding was that competitive adsorption between water and trace contaminants of VOCs has a significant effect on the oxidation rate.. 1995). Table 7 presents a comparison of photocatalytic oxidation. indoor air. A TiO2-coated fibre glass mesh composed of anatase TiO2 and SiO2 was first employed for photocatalytic oxidation of benzene. benzene. The nanoscale photocatalysts were composed mainly of mesopores with pore size in the range of 35–44 nm. Using platinum loaded on TiO2 could facilitate the removal of poisonous intermediates from the deactivated TiO2 surface but resulted in lower oxidation rates of toluene. different organic compounds have been tested and they usually exhibit different photodegradation rates.. they later developed nanoscale TiO2 photocatalysts using the acid-assisted sol–gel technique. ultrasmall SnO2 with a diameter of 5 nm exhibited initial photoactivity as high as 3 times than that of P25 TiO2 (30 nm) in the absence of water vapour whereas larger size particle SnO2 (22 nm) did not show photoactivity.. and acetone in the ppb concentration range.75 ppm.. (b) oxidation of donor (D). O3 addition in O2 markedly increases the mineralisation percentage of n-octane. Cao et al. titania on glass-plate reactor (Obee. (d) and (e) electron–hole recombination at surface and in bulk. 2000). 1999a). 3). The results show that photodegradation of acetaldehyde is lower than that for formaldehyde and acetone. They found that adsorption of benzene on the surface of TiO2 appeared to be promoted by the presence of UV-light. formaldehyde.

The experimental Table 7 Conversions of several VOCs using TiO2 under different reactor configuration (Jo and Park. (2000) Pichat et al. (2000) Jo et al. IPS: inlet port size.8%) m-Xylene TiO2 (6. They further extended the investigation to chlorinated VOCs. (2002) Jo et al. The 1. (2002) Jo et al.. (1998) Stevens et al. (2005b) 699 TiO2 (5%) TiO2 (5%) TiO2 (5%) Formaldehyde 356 Acetaldehyde Acetone 356 356 365 365 365 365 352 352 352 352 TiO2 (6. / Environment International 33 (2007) 694–705 Table 6 Comparison of catalyst system for VOCs degradation under UV-light Catalyst VOC λ Initial Conversion Reference (nm) concentration (%) (ppb) 15 15 15 15 40 60 20 93 78 78 45 21 20 20 20 20 77 23 88 80 65 60 23 23 23 80 60 100 30 50 55 50 100 100 100 100 100 70 80 88 88 82 84 5 24 48 54 4 30 22 Stevens et al. (2000) Pichat et al. (1998) Pichat et al.0 77 86 88 85 89 88 70 73 76 72 82 84 Individual La (1. (2002) Jo et al. and IPS (4.p-Xylene o-Xylene PCE TCE 68 79 84 75 84 84 RH: relative humidity. 2004) Compound Mixture RH (%) 10– 20 40– 60 a 71 81 82 79 85 82 80– 100 67 80 83 80 84 80 HD (mm) 5. (2005) Strini et al. (2005b) recently reported the preparation of Ln3+ doped TiO2 catalysts for enhanced photocatalytic oxidation of benzene. 4). HD: hydraulic diameter. Two types of lanthanide ion-doped titanium dioxide. Wang et al. ethylbenzene and o-xylene (BTEX) for indoor air purification. a The HD (20 mm). Shiraishi et al. (2005b) Li et al. The enhanced photodegradation of BTEX is possibly due to the improved adsorption ability and the enhanced electron–hole pairs separation due to the presence of Ti3+ on the surface of Ln3+–TiO2 catalysts and the electron transfer between the conduction band/defect level and lanthanide crystal field state (Fig. toluene. The PCO destruction of VOCs was up to nearly 100%. La3+–TiO2 and Nd3+–TiO2.8%) Benzene TiO2 (6. (2005) developed a high-performance photocatalytic reactor with a parallel array of nine light sources for photocatalytic decomposition of gaseous HCHO at a very low concentration using amorphous TiO2.2% Ln3+–TiO2 catalysts achieved the highest photocatalytic activity. and the CO generated during PCO was a negligible addition to indoor CO levels (Jo and Park. RM (glass). o-xylene (triangles) and both m. (2002) Jo et al.8%) o-Xylene TiO2 (20%) TiO2 (20%) TiO2 (20%) TiO2 (20%) TiO2 (20%) TiO2 (5%) TiO2 (5%)/AC TiO2 (5%) TiO2 (5%)/AC TiO2 (20%) TiO2 (20%) TiO2 (1%) TiO2 (1%) TiO2 (1%) TiO2 (1%) TiO2 (5%) Benzene m-Xylene p-Xylene o-Xylene Fig. The photocatalytic efficiency of the TiO2 catalysts with the lanthanide ion doping was remarkably enhanced by BTEX removal.S. trichloroethylene (TCE) and perchloroethylene (PCE) under non-occupational indoor air quality. Benzene Ethyl benzene m. Li et al.and p-xylene (squares) in a non-air tight room caused by the prototype air purifier. but dependent on the hydraulic diameter (HD) and flow rate (FW) of the reactor. (2005) Strini et al. 3. t = o refers to the concentrations before the purifier UV lamps were switched on (Pichat et al.0 mm) were employed. (1998) Stevens et al. (2000) Pichat et al. (2005b) Li et al.8%) p-Xylene TiO2 (6. (2005) Li et al. toluene (diamonds). were prepared by a sol– gel method. 2004).0 99 99 97 99 95 99 RM Stainless steel 79 88 87 85 92 90 IPS (mm) 2. Decreases in the concentrations of benzene (crosses).2%)/ Benzene TiO2 (5%) Nd (1. The destruction of aromatic VOCs was independent of humidity. (2002) Ao and Lee (2003) Ao and Lee (2003) Ao and Lee (2003) Ao and Lee (2003) Jo and Park (2004) Jo and Park (2004) Strini et al. .2%)/ Benzene TiO2 (5%) close to 100%. (2005) Strini et al. 2000). RM: reactor material. Ethyl benzene 352 Benzene Benzene Toluene Toluene PCE TCE Benzene Toluene 365 365 365 365 352 352 355 355 Ethyl benzene 355 o-Xylene Benzene 355 365 365 365 Apart from the commercially available TiO2.

In order to make TiO2 effective under visible light. may then appear as an appealing challenge for developing the future generation of photocatalytic materials. reported an investigation for photodegradation of benzene. 2004). To avoid deactivation of photocatalyst and increase the photocatalytic degradation rate of contaminants. 4. such a research is limited in the literature. 3. It has been found that the rate of PCO decreased with decreasing pollutant concentration. However. 2005). Shen and Ku (2002) studied the decomposition of gas-phase TCE by the TiO2/UV process in the presence of ozone. of the visible region of the spectrum. Anpo and Takeuchi (2003) have summarised the work in this area. It was discovered that metal-ion implantation with various transition-metal ions such as V. Few TiO2 catalysts exhibit high activity for VOC degradation under visible light. Chapuis et al. Recently. Wang et al.700 S. a complete mineralisation is achieved even over Hombicat UV100. a lot of investigations on photocatalytic oxidation of VOCs have been conducted and most of research focus on TiO2 -based catalysts. They found that Degussa P25 appeared more active than Hombicat UV100. However. excluding the transmitted photons. They found the addition of ozone into the TiO2/UV/TCE system with 254 or 365 nm UV lamps reduced the removal of TCE. and Ni accelerated by high voltage makes possible a large shift in the absorption band of the titanium oxide catalysts toward the visible-light region. Cr. (2002) found that. toluene. 2003.2 eV and therefore it cannot be used indoors or inside vehicles. (Zhang et al. 2005b). 2004). for the photonic efficiency taking into account the absorbed and scattered photons only and. another method has been made by addition of other oxidants such as ozone. All above investigations with artificial UV-light has been demonstrated. Visible-light irradiated catalysts for VOCs As shown above. However. the photocatalytic activity observed for the pure titanium dioxide sample was higher than cementitious samples with 3% catalyst content (Strini et al. In addition. Degussa P25 and Hombicat UV100. The practical evaluation by installation of the TiO2/AC filter in an air cleaner was also conducted. and Cr2O3. CoO. (2005) explored the photocatalytic activities of two commercial TiO2 catalysts. The cementitious photocatalytic material showed an interesting photocatalytic activity with linear dependence versus pollutant air concentration and irradiance. To improve this situation. residence time: 72 s by using different catalysts at a same humidity level: 15700 ppm v− 1 (Li et al. CuO. Zhang and Liu. with differing levels of effectiveness. NiO. result indicates that this photocatalytic reactor can rapidly decompose HCHO toward zero concentration. possibly because excessive ozone molecules could scavenge hydroxyl radicals produced from the excitation of TiO2 by UV radiation. The study showed that the enhancement effect of the TiO2/AC shown in the laboratory scale using the photoreactor was also achieved by installing it into an air cleaner available in the commercial market (Ao and Lee. (2002) explored microemulsion method to prepare heavily cation doping TiO2 . at high humidity levels. For 580 ppm.. metalion-implantation method has been widely used to modify the electronic properties of bulk TiO2 photocatalysts by bombarding them with high-energy metal ions. Solar photocatalytic degradation of formaldehyde in the gaseous phase has been investigated by Ching et al. TiO2 will exhibit much lower catalytic conversion. The efficient use of solar light or. TiO2/UV and O3/TiO2/UV were studied by Zhang et al. steady state conversions of less than 95% are attained.. for n-butanol decomposition under visible light. but at 145 ppm. conventional TiO2 photocatalysts are utilised only under UV-light due to its wide band gap of 3. ethylbenzene. However. ethylbenzene and o-xylene at ppb level by titanium dioxide dispersed in cementitious materials. Photocatalytic removal percentage of benzene. Strini et al. Fuerte et al. / Environment International 33 (2007) 694–705 Fig. 2005). in other words. they also developed a new alternative method for directly preparing visible-lightresponsive TiO2 thin film photocatalysts by applying a RF magnetron sputtering deposition method. Kirchnerova et al.. Mn. However. The degradations of trace hexane and toluene in the gas phase by O3/UV. 2003). if doped with some metal oxides such as Ag2O. (2004). The use of TiO2/AC not only increased the target pollutant removal efficiency but also reduced the amount of intermediate exiting the system. In addition.2. and o-xylene in the continuous gas flow reactor with an initial concentration: 23 ± 2ppb v. The experimental results showed that the addition of ozone to the photocatalysis process could greatly increase the conversion of hexane and toluene and the deactivation of the photocatalyst at high inlet concentration of toluene was avoided in the presence of ozone. The removal efficiency of TiO2/AC was seven times higher than TiO2 only under high humidity levels for multiple indoor air pollutants removal (Ao and Lee. water vapour competed with TiO2 for adsorption sites which further decreased the rate of PCO. the thin film has a higher value. in other words. toluene. Ao and Lee developed an activated carbon filter immobilised with TiO2 (TiO2/AC) to overcome the competition effect between the water vapour and the pollutant at ppb level for indoor air purification (Ao and Lee. Fe. It is found that the sol–gel TiO2 thin film has a lower apparent photonic efficiency of solar photocatalysis than a Degussa P25 TiO2 coating. The application has the potential to be made more economical if the artificial UV is replaced by solar UV.

5.. 2005a). higher specific surface area. Br−. I−) (Belver et al. a representative example of volatile organic compound (VOC) present in urban atmospheres. (2005) Kirchnerova et al.. 2001.. (2006) Wang et al.. such as N3−. One new approach to produce visible-light activated TiO2 photocatalysts is by doping with anions. no correlation between N-concentration and photocatalytic activity was observed (Li et al.. Consequently. A series of nanosized N-containing TiO2-based materials was also tested in the photocatalytic degradation of methylcyclohexene. the ZrO2-modified TiO2–xNx displays higher porosity. However. The NTO powder prepared from a mixed solution of TiCl4 and NH4F demonstrated the highest photocatalytic activity among three Nprecursors. Acetaldehyde and trichloroethylene decompositions were used as probe reactions to evaluate the photocatalytic activity of these NTO powders under visible-light (vis) irradiation. 2004) and acetone (Ihara et al. leading to the formation of ring-opening products such as carboxylic acids and aldehydes. (2003) Wang et al.. Irokawa et al. Mesoporous nanocrystalline TiO2–xNx and TiO2–xNx/ZrO2 visible-light photocatalysts have been prepared by a sol–gel method. Cl−. guanidine. (2003) prepared N-doped TiO2 (NTO) powders using TiCl4 and an Nprecursor (urea. C4−. The photocatalytic activity of the samples was evaluated by the decomposition of ethylene in air under visible-light (lambda N 450 nm) illumination. Asahi et al. first reported the visible-light photocatalysis in N-doped TiO2 (Asahi et al. (2005) Rodrigues et al. (2005a) Li et al. Many investigations have described the enhanced photocatalytic properties of titania by nitrogen doping. 2003) upon irradiation of visible light. This high photocatalytic activity was ascribed to a synergetic effect of several factors: its porous and acidic surface. (2005) Subscript indicates the reaction time (hour). (2005a) Rodrigues et al. resulting in high visible absorption. The photoactivity increases with W content and is much better than TiO2 itself and TiO2 P25.. 2001). 2005). 2-propanol (Miyauchi et al. (2001) Asahi et al. It is also found that N-precursor also affects the surface morphologies of N-doped TiO2 particles. Wang et al.. (2006) Li et al. . and simultaneously co-doped F atoms during nitrogen introduction. Photocatalytic activity of MCM-48 mesoporous materials for the degradation of acetaldehyde in air under visible light (Rodrigues et al. is initially photooxidised to benzaldehyde which adsorbs onto the TiO2–xNx surface more strongly.S. S4− or halides (F−. Results obtained indicate that toluene. / Environment International 33 (2007) 694–705 701 Fig. The introduction of ZrO2 into TiO2–xNx considerably inhibits the undesirable crystal growth during calcination. Major intermediates adsorbed at the catalyst surface were gradually photodegraded to CO2 and H2O under visible-light irradiation (Irokawa et al. and it was much higher than that of commercial P25. Recently. (2006) Irokawa et al. weakly adsorbed on the catalyst surface. VOC n-Butanol n-Butanol Acetaldehyde Acetaldehyde Acetone Ethylene Ethylene Toluene Acetaldehyde Tricholoroethylene Acetaldehyde Tricholoroethylene Acetaldehyde Acetaldehyde λ (nm) 380 380 436 436 470 450 450 420 420 420 420 420 – – Initial concentration (ppm) 145 580 485 485 21 227 227 20 930 943 930 943 328 328 Conversion a (%) 95 100 85 495 10036 351 521 10013 323 183 653 373 382 1002 Reference Kirchnerova et al. oxides and found that nanosized Ti–W mixed oxides are effective in photocatalytic degradation of toluene using sunlight-type excitation. 2006a). Ihara et al. They used toluene as test compound.. It was found that the samples contain substitutional and interstitial N-containing impurities and a significant number of oxygen vacancies. 2006). or ammonium fluoride). It was suggested that these species substitute the oxygen lattice on TiO2 and lead to a band gap narrowing. (2001) Ihara et al. These catalysts were found to photodegrade gaseous acetaldehyde (Asahi et al. and an improved thermal stability over the corresponding unmodified TiO2–xNx samples (Wang et al. doped N atoms. They tested various TiO2–xNx catalysts for VOC decomposition. (2005) Asahi et al. (2005a) Li et al. reported the photooxidation of aromatics over nitrogen doped TiO2 (TiO2–xNx) under visibleTable 8 Comparison of catalytic activity of various catalysts under visible light Catalyst TiO2 TiO2 TiO2 TiO2–N TiO2–N TiO2–N TiO2–N/ZrO2 TiO2–N TiO2–N TiO2–N TiO2–N–F TiO2–N–F Cr/MCM-48 Ti–Cr/MCM-48 a light irradiation. (2005a) Li et al. 2006).

However. 4. TiO2 þ hν→hþ þ e− hþ þ OH− →U OH ð 1Þ ð 2Þ . (Jo et al.. Ao et al. however. 2002). Another investigation using Ln3+– TiO2 as the photocatalyst demonstrated that NO could slightly promote the BTEX removals (Li et al.. The inhibition effect of SO2 is due to the sulfate ion competing with the pollutant for adsorption sites on TiO2. above and below which a decrease of the steady state reaction rate is observed. Cao et al. also investigated the effect of humility on activity of TiO2 and SnO2 in 1-butene photooxidation and reported that the oxidation rate on SnO2 drops dramatically with increasing moisture in the feed steam. 3-butadiene on titania. UV lamp was turned on at 181 min (Jo et al. 2006b). In the absence of water vapour. Fig. The surface of TiO2 catalysts is abundant in hydroxyl groups. 2002. Zhang et al. 2004). Table 8 presents a summary of VOC conversion over photocatalysts effective under visible light. In contrast. The presence of other gaseous pollutants will also influence VOC photodegradation. Jo et al. 6. The high activity of the photocatalyst is attributed to the synergistic interaction between the Cr ions dispersed in the silica framework and the nanocrystalline nature of titania crystallites anchored onto the pore walls (Rodrigues et al. ethyl benzene. It is seen that Ndoped TiO2 generally exhibits higher activity and doping with additional components will further promote the catalytic activity. The data showed that competitive adsorption between water and trace contaminants has a significant effect on the oxidation rate. Obee and Brown presented an investigation of the effect of humility on photooxidation of formaldehyde. 2000). / Environment International 33 (2007) 694–705 Photocatalytic activity is correlated with an optimum of oxygen vacancies. 5 presents a comparison of different MCM-48 based catalysts for visible-light degradation of a typical indoor air pollutant. 1999b). Further investigation on TiO2/AC system shows similar results (Ao and Lee. 2003). 2003)... and perchloroethylene. while very poor photoactivity is observed after the water concentration increases up to 2000 ppm. they could react with BTEX and enhanced their conversion (Ao et al. The oxidation rate increases with decreasing humidity for humidity levels above ca. High photoactivity of SnO2 is only apparent at low water vapour level (b 1000 ppm). acetaldehyde. 6 shows the VOC concentrations measured prior to and after turning on the UV lamp for four different RH ranges.g.. Ti–Cr–MCM-48 showed the highest activity. The PCO destruction efficiencies were close to 100% for four different RH ranges from 18 to 78%. NO in the air would promote the conversion of BTEX. the photocatalytic degradation of some chemical compounds (e. which leads to adsorbing water via hydrogen bonding or aromatics via an OH–π-electron-type complex. Fig.. 2005b). and 1. The physico-chemical bases of this behaviour are discussed on the light of the above mentioned experimental results (Belver et al. formaldehyde) is seriously retarded and the total mineralisation to CO2 does not occur. (2004) reported that the presence of SO2 decreased the conversion of BTEX by more than 10% on TiO2. Jo and Park. investigated the photocatalytic oxidation of toluene and hexane under TiO2/UV and O3/TiO2/UV conditions. Wang et al. excessive water vapour on the catalyst surface will lead to the decrease of reaction rate because water molecules can occupy the active sites of the reactants on the surface (Zhao and Yang. and o-. 1000 ppm v− 1 The dependencies of humidity and contaminant concentrations on the oxidation rates are explained as being the results of competitive adsorption on available hydroxyl adsorption sites and of changes in hydroxyl radical population levels. Ao and Lee (2003) compared the effect of humidity on photocatalytic oxidation of BTEX on TiO2 and TiO2/AC systems and the results indicate that TiO2/AC exhibits higher resistance to humidity effect. Nanoscale TiO2 catalysts exhibited both Fig.702 S. Since the hydroxyl radicals were generated during the photodegradation of NO. higher activity and stronger resistance to the negative effect of humidity (Cao et al. 2005). m-. 2004) found that the humidity had little effect on photocatalytic oxidation of benzene.. 5. Their researches show that the conversions of toluene and hexane initially increased with increase of relative humidity up to 40% and then show decrease. However. A Ti–Cr photocatalyst based on mesoporous MCM-48 prepared in a single step exhibits superior photocatalytic activity compared to TiO2–Cr–MCM-48 prepared by a post-impregnation method. Effect of water vapour and other gaseous compounds on photocatalytic oxidation The influence of water vapour on the performance of titania oxide catalyst depends on the level of water. TiO2 films maintain a stable oxidation rate even though the water concentration varies from 0 to 3000 ppm. Reaction mechanism and kinetics It is generally believed that the initial stages concerning photocatalysis processes are as below (Cao et al. toluene. PCO destruction of benzene for four different RH ranges. toluene. p-xylenes. Widely differing effects of water vapour have been reported. Their further investigation on ethylene oxidation on titania also indicates the similar conclusion (Obee and Hay.. trichloroethylene.. 1997).

The main oxidation product was benzaldehyde. Obee. few investigations on the kinetics of VOC photocatalysis for indoor air are reported. benzyl alcohol. Blount and Falconer (2001) characterised the intermediates after PCO of toluene on TiO2 using temperature programmed hydrogenation and found that toluene reacted through benzaldehyde in more than one form on TiO2 and that these forms had different reactivities during PCO.796 1-Butene 1-Butene 0. Adsorption of butene B þ S↔B S Surface reaction B S→P þ W S Desorption of water W S↔W þ S : : : : ð13Þ ð14Þ ð15Þ Reaction kinetics gives information about the reaction rates and the mechanisms by which the reactants are converted to the products. The intermediates and/or by-products were extracted from the TiO2 surface by aqueous NaOH solution. In practical research. Augugliaro et al.S. In their other investigation on PCO of toluene and formaldehyde. Few investigations have been reported on reaction mechanism. / Environment International 33 (2007) 694–705 703 Ti4þ þ e− →Ti3þ Ti U 3þ ð3Þ 4þ þ O2ads →Ti þ O− 2ads ð4Þ ð5Þ ð6Þ Table 9 Langmuir–Hinshelwood coefficients for various VOC reactants Catalyst VOC TiO2 TiO2 SnO2 TiO2 Ethylene K0 (μmol/ Kw cm2/h) (ppm− 1) 0. Different intermediates will be produced depending on the U VOCs and these intermediates will be further oxidised by O2 or U O to produce CO2. r ¼ k0 Kc XE ð1 þ Kc XE þ Kw Xw Þ ð11Þ where k0 (μmol/cm2/h) is the rate constant for a given UV intensity (I ). they used a Langmuir Hinshelwood (L–H) rate form for bimolecular surface reactions (Obee and Brown. The kinetic parameters are presented in Table 8. Although many studies have investigated the gas-phase PCO of various VOCs on TiO2 and other catalysts. Wang et al. Herrmann (2005) discussed the major physical parameters influencing the photocatalytic kinetics.85 Obee and Hay (1997) Obee and Brown (1995) Cao et al. Formic acid was produced during the reaction and the major oxidative and reductive processes in the photodegradation of formaldehyde can be written as follows: TiO2 Y e− þ hþ Oxidation HCHO þ H2 O þ 2hþ →HCOOH þ 2Hþ HCOOH þ 2hþ →CO2 þ 2Hþ Reduction O2 þ 4e− þ 4Hþ →H2 O ð10Þ ð8Þ ð9Þ hγ and (v) the radiant flux. Ching et al. (iii) partial expression and/or concentrations of reactants.36 0. and malonic acid as possible intermediates.3-Butadiene 0. (ii) wavelength. (1999b) Cao et al. (1999) used FT-IR for mechanistic investigation PCO of toluene and reported the detection of benzaldehyde. and the extracts were analysed by HPLC. and XE (ppm v− 1) and XW (ppm v− 1) are the gas-phase concentrations of ethylene and water vapour. Table 9 presents some results of the kinetic studies. Their analysis identified phenol.00818 0. However. Obee and Hay (1997) used the following L–H model to describe the kinetics of ethylene photodegradation and obtained the activated energy of 1. they have focused on PCO rates rather than on the identification of adsorbed intermediates and surface processes.63 0. hydroquinone and/or benzoquinone. CO2.1 1. (1999b) OH þ pollutant→oxidised pollutant þ h þ e→thermal heat or luminescence 1. benzene. (1998) studied the photocatalytic degradation of gaseous formaldehyde on a TiO2 thin film.00045 0. These are (i) mass of catalyst. Noguchi et al.00749 0. kinetic experiments are performed to study the photodegradation of the objective compounds. Jacoby et al. respectively. and trace amounts of benzoic acid and phenol during PCO of a continuous flow of toluene over TiO2. (1999b) used the following L–H mechanism and derived the kinetic model for PCO of 1-butene on SnO2 and TiO2 film. Kc and KW (ppm v− 1) are the Langmuir adsorption equilibrium constants.14 Hydroxyl radicals and super-oxide ions are highly reactive species that will oxidise VOCs adsorbed on the catalyst surface.7 kcal/mol. (iv) temperature (at a second degree) Zhang and Liu (2004) investigated the kinetics of photocatalytic degradation of hexane on TiO2 with and without ozone.24 0. For a heterogeneous reaction.045 12. 1995.000458 Kc Reference (ppm− 1) 0. 1996) as follows: r ¼ k0 K1 Xc K4 Xw ð1 þ K1 Xc þ K2 Xw Þ ð1 þ K3 Xc þ K4 Xw Þ ð12Þ ð7Þ Cao et al. (1996) investigated the PCO of benzene on TiO2 and extracted adsorbed intermediates following PCO. (2004) also investigated the kinetics of PCO of formaldehyde and found that a pseudo-first-order expression . They compared three types of L–H kinetics and found that the kinetics with bimolecular surface and competitive adsorption of water and hexane on TiO2 would be the best one for PCO without ozone. a Langmuir–Hinshelwood (L–H) rate form was widely found to provide a good correlation to the oxidation rate data.

/ Environment International 33 (2007) 694–705 could be applied if the reactant concentration is low.109:113–39. Recently. the produced intermediates can be more toxic to human health and should be removed or further oxidised to CO2.14:55–68. Combination effect of activated carbon with TiO2 for the photodegradation of binary pollutants at typical indoor air level. These airborne pollutants can be emitted from diverse sources and a long-term exposure to these air toxics will cause health problem known as SBS. Synthesis and solid characterization. J Catal 1999a. J Catal 2001. et al. cars and transportation cabins. Ao CH.704 S. Spiess FJ. Brown SK. Wang et al. Falconer JL. Lee SC. few investigations have been conducted in this area. Fernandez-Garcia M. Morikawa T. Chem Eng Sci 2005. Ao CH. Proceedings of National Clean Air Conference 2003:23–7 Newcastle. Photocatalytic behavior under sunlight excitation.212:1–9. Belver C. Blount MC. 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