Journal of Materials Chemistry

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FEATURE ARTICLE

Self-cleaning bers via nanotechnology: a virtual reality

Wing Sze Tung and Walid A. Daoud*
Received 10th November 2010, Accepted 11th March 2011 DOI: 10.1039/c0jm03856c With the fast-growing demand toward innovative functional and intelligent brous materials, the photocatalytic self-cleaning surface functionalization of bers has universally aroused tremendous interest in recent years. Due to the promising properties of nanosized photosensitive substances in decomposing undesirable contaminants, intensive research has incessantly been conducted to explore their multi-functional properties and potential applications. This review paper intends to summarize recent developments of contemporary technologies, particularly emphasizing on the progress achieved in the past ve years in the application of nanostructured titanium dioxide photocatalyst in brous materials. The fundamental concepts, limitation, societal impact and future prospects are also discussed.

Introduction
With the increasing demand for functional brous materials, where bers not only have the basic characteristics, but also possess environmentally friendly functionalities such as selfcleaning, antimicrobial, and anti-pollution, self-cleaning coating

School of Applied Sciences and Engineering, Monash University, Churchill, VIC, 3842, Australia. E-mail: Walid.Daoud@monash.edu; Fax: +61 3 990 26738; Tel: +61 3 990 26411

Wing Sze Tung is a nal year PhD student at Monash University in the eld of Materials Science. She received her Bachelor degree in textile technology in 2006 from the Hong Kong Polytechnic University. Her research work has been mainly in the areas of nanotechnology, photocatalysis, visible light photocatalysis and keratin surface modication.
Wing Sze Tung

Dr Daoud is a Senior Lecturer at Monash University. He graduated from University of Technology Graz, Austria with a Dipl-Ing degree (BS and MS) in Chemical Engineering and received his PhD in the fabrication of bilayer photovoltaic devices from the University of Shefeld. He then joined Possehl Besi Precision Machinery Hong Kong in the semiconductor substrate industry as Walid A: Daoud a process development engineer to establish a prototype reel-toreel photoresist coating for high-precision plating. In 2002, he was offered a postdoctoral position at Hong Kong Polytechnic University (HKPU), where he played a substantial role in the establishment of a Nanotechnology Center in 2003 which earned him a research fellowship and a lectureship at HKPU before moving to Monash University in 2007. His main research interests are photocatalysis, reactor engineering, sensors and actuators, and energy harvesting materials. His research has attracted wide interest in the community through esteem factors, popular science and the press.
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technologies are developing rapidly at present, with a particular focus on self-cleaning brous materials. Self-cleaning surfaces can be classied as hydrophobic or hydrophilic. The former, also popularly known as the lotus effect, can be achieved by chemical or geometrical surface modication. The mechanism is that by mimicking the surface natural features of lotus leaves or buttery wings, surface-attached dirt or ne debris can be removed through the action of rolling water droplets off their hydrophobic surface, hence the cleanliness of the material can be maintained.1,2 On the other hand, hydrophilic self-cleaning, also known as the photocatalytic effect, is a chemical surface modication that uses photoactive substances to induce catalytic purication functions on a substrate surface. These substances chemically decompose adsorbed dirt, contaminants, pollutants or microorganisms through photooxidation and photoreduction reactions in the presence of light.3,4 Moreover, hydrophilic self-cleaning materials not only induce self-cleaning functions, but also confer additional properties such as antimicrobial and deodorization.3,4 Owing to the signicant potential of photocatalytic self-cleaning brous materials in the global commercial market, the selfcleaning surface functionalization of bers has universally been receiving increasing attention. Following recent reports on incorporating nanostructured photocatalysts into exible substrates,511 several studies on the deposition of titanium dioxide particles on brous materials have been carried out using various application methods, such as hydrothermal treatment,5 solgel processing,57 impregnation,8 liquid phase deposition,9 chemical spacers10 or sputtering.11 Although thermally resistant solid materials such as glasses, tiles, silica, ceramics, and quartzes3,4,12 have been identied as suitable base substrates for exploring the potential application of titanium dioxide photocatalyst, the technologies of grafting titanium dioxide on exible substrates, such as fabrics, plastics, textiles, and papers are limited due to their low chemical and thermal resistance against the post-deposition high-temperature treatment required to promote high crystallinity of the grafted catalyst.511,1315 Moreover, the low surface energy of exible substrates and their often irregular shapes pose one of the hardest challenges in achieving sufcient interfacial adhesion. Hence, the self-cleaning bers concept continues to bring in opportunities for future research and development. In this review, current state-of-the-art photocatalytic self-cleaning surface functionalization technologies are reviewed, focusing on recent key developments of self-cleaning brous materials and their numerous potential applications. The limitations and future prospects of this research are also discussed.

Photocatalytic self-cleaning surface functionalization treatment

Historical background of photocatalysis Photooxidation of an organic substance, chlorazol sky blue, through photosensitization of titanium dioxide at l 365 nm was rst reported by Goodeve and Kitchener in 1938.16 Later on, Kato and Mashio,17 and Filimonov18 extended the study to tetralin and 2-propanol using titanium dioxide and zinc oxide in 1964.17,18 Shortly thereafter, a breakthrough was brought in by
This journal is The Royal Society of Chemistry 2011

Honda and Fujishima who,19 inspired by photosynthesis in plants, investigated photoelectrolysis of water (water splitting) with light energy. They discovered that water can be decomposed into oxygen and hydrogen through photoelectrochemical reaction in the presence of ultraviolet-visible light using rutile titanium dioxide as the anode and platinum as the counter electrode in aqueous electrolyte solutions.3,4,19 In 1972, the conception of solar-activated electrochemical photolysis of ware demonstrated that titanium dioxide semiconductor could be used as an environmental friendly photocatalyst for solar-assisted energy conversion.19 Inuenced by Frank and Bard, who were the rst to investigate the decomposition of toxic cyanide in water by photocatalysis with titanium dioxide in 1977,20 the detoxication of organic pollutants using titanium dioxide powder without platinization, by way of a photocatalytic process under ambient condition, has attracted worldwide attention. In the middle of 1980s, the fanaticism of using titanium dioxide electrode as a tool for hydrogen production was shifted due to a number of challenges, such as instability, low efciency and lack of reproducibility.3 Simultaneously, scientic studies on titanium dioxide as a multifunctional photocatalyst had started. Later on, research on photocatalysis focusing on pollutant removal blossomed particularly in the treatment of wastewater and polluted air. Nevertheless, titanium dioxide photocatalysis was not commercially attractive due to the low quantum efciency caused by immature synthesis technologies and thus almost none of these developments had been commercialized.3,4 Since the discovery of photocatalysis, scientists mostly focused on exploring the potential of titanium dioxide in environmental applications, while the feasibility and compatibility between titanium dioxide, photocatalytic technologies and substrate substances had been overlooked. Until 1990s, there was an increasing interest in the concept of photo-induced self-purication materials through the incorporation of photocatalysts in various substrates in order to introduce a function of disinfection, primarily for water and air treatments.21,22 Knowing its potential in maintaining cleanliness of a surface, the utilization of titanium dioxide coating as self-cleaning surface was explored. The rst photocatalytic self-cleaning ceramic was realized by Fujishima et al.23 and Heller24 concurrently in early 1990s. Many researchers and investors conceived similar ideas to explore a number of self-cleaning products, such as self-cleaning lamp covers, self-cleaning glasses, self-cleaning window blinds, selfcleaning tents, etc.4 With more photocatalytic-products available, new application areas have been exploited. In 1995, Fujishima research group, in collaboration with TOTO Ltd., Japan, accidentally discovered that titanium dioxide possesses a high photo-induced hydrophilicity after light irradiation, which widened the application of the photocatalyst as surface coating.3,25 Ever since, industrial products using photocatalytic surface functionalization treatment are marked as hydrophilic self-cleaning coating. Three years later, the photocatalytic antimicrobial property of titanium dioxide-coated materials was ascertained, in which Escherichia coli (E. coli) could be completely decomposed by titanium dioxide under UV irradiation.26 In the twenty-rst century, advanced photocatalytic technologies have been continuously pursued. However, the application
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has greatly been limited due to the high temperature required in the application process.13,14 Until 2004, with the aid of an advanced bottom up nanotechnology approach and the solgel process, Daoud and Xin rst fabricated self-cleaning cotton through in situ nucleation and growth of anatase titanium dioxide at low temperature and ambient pressure.27 Since then, numerous photocatalytic self-cleaning surface functionalization processes have been proposed for low thermally resistant materials.611 Photocatalyst-substrate adhesion, coating homogeneity and photocatalytic efciency are greatly dependent on the base substrates. With further improvement of the photocatalytic self-cleaning coating techniques,511,27 the application of homogenous titanium dioxide coating in different types of materials with reproducible photoactivity has become possible. On the other hand, many endeavors have been devoted to improve the photocatalytic properties of titanium dioxide.2830 Methods such as dye/surface sensitization, selective ion doping, composite semiconductor coupling, surface chelation and derivatization have been widely explored,2932 particularly in (1) extending the effective absorption range of titanium dioxide from ultraviolet to visible-light region; (2) suppressing the recombination of the generated electronhole pairs through enhancing the charge separation; and (3) modifying the quantum efciency of the heterogeneous photosensitive catalysts.31,32 To date, attempts are still being dedicated to produce stable visiblelight photocatalysts with efcient photochemical reactions in diverse applications. Mechanisms of photocatalysis Heterogeneous photocatalysis is a photo-assisted catalytic process utilizing a substance that converts light energy into catalytic work through chemical reactions. The photocatalyst acts as a photosensitive substance which possesses a strong oxidation effect with the aid of light energy. The basic mechanism of photocatalysis is contributed by the promotion of electrons from the valence band to the conduction band of the photocatalyst on absorption of light, provided that the energy absorbed from the light source is equal to or greater than the band gap energy (i.e. hv > DE) of the photocatalyst.3,4,33 As shown in Fig. 1, under normal conditions and without photonic excitation, the photocatalyst is at the ground state where electrons are localized in the valence band. However, upon photo-excitation, electrons get sufcient energy to overcome the band gap barrier and move to the conduction band. Activated photocatalysts generate electronhole pairs in the presence of

a light source, where highly active electrons (e) form in the conduction band and positive holes (h+) in the valence band. The formed photogenerated electronhole pairs can react in three possible pathways as illustrated in Fig. 2. (1) Electronhole pairs rapidly recombine on the surface or in the bulk of the photocatalyst (recombination); (2) electrons diffuse to the surface of the photocatalyst and react with adsorbed oxygen molecules producing reactive oxygen radicals (O, O2, O3) (photoreduction); and (3) holes oxidize water molecules or adsorbed hydroxide ions forming highly oxidizing hydroxyl radicals (OH) (photooxidation). The radicals generated from the reaction of electronhole pairs contribute to the powerful photo-electrochemical reactions that are capable of decomposing attached dirt, harmful microorganisms and organic contaminants into carbon dioxide and water without the application of an external voltage at ambient temperature according to the following equations.3,4,19,33 TiO2 + hn / e + h+ e + h+ / TiO2 e + O2 / O2
+ _ O 2 + H / HO2

(1) (2) (3) (4) (5) (6)

h+ + H2O / _OH + H+ _O h+ + O 2 / 2

Fig. 1 Schematic diagram of photo-excitation process on TiO2 surface.

Fig. 2 Schematic diagram of TiO2 photocatalysis.

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Titanium dioxide photocatalyst Materials, which are able to catalyze reactions with the involvement of light illumination, are known as photocatalysts. There are many photosensitive substances such as SrTiO3, SnO2, ZrO2, ZnO, ZnS, CdSe, CdTe, WO3 and Fe2O3 with small band gap or good light absorption which may work well as photocatalyst. However, studies showed that titanium dioxide has several advantages over all others.34 Not only because it has strong oxidizing ability but also because it is highly stable due to the inactivity of electrons in the absence of illumination. From an economic point of view, titanium is the fourth abundant elements in earth, thus, titanium dioxide possesses potential because of its availability and inexpensiveness. Besides, the range of applications, such as cosmetics, paint and even food additives, gives evidence that titanium dioxide is innoxious. On top of that, titanium dioxide is superhydrophilic and forms a sheet-like layer of moisture upon light exposure and presence of water, which can act as a transparent protector against dirt.3437 Thus, titanium dioxide photocatalyst can be utilized in applications such as self-cleaning, anti-fogging, antimicrobial, deodorization, and wastewater remediation. Titanium dioxide photocatalyst, also known as titanium(IV) oxide or titania, is found in three common crystalline forms, namely anatase, rutile, and brookite. Amongst the several polymorphs of titanium dioxide, anatase has proved to be the most photocatalytically active.38 Besides, it has been shown that the decrease in the diameter of titanium dioxide particles increases the photocatalytic activity due to a larger surface area per unit mass and volume.39 In the commercial sector, Degussa P-25 (P-25), composed of 70% anatase and 30% rutile, is a benchmark titanium dioxide catalyst due to its advanced photocatalytic ability. However, the application of P-25 is hindered due to its limited dissolution property. Intensive efforts have been incessantly dedicated in exploiting other titanium dioxide synthesis approaches to surpass P-25. Titanium dioxide, in form of powder, solution, gel, and paint material, can be synthetically obtained by a number of methods such as solgel process, chemical vapor deposition, impregnation, anodic oxidation and sputtering in present industries.35,36,4042 Owing to the above-mentioned properties and virtues, titanium dioxide has been the most commonly used photocatalyst in self-cleaning coatings.

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Fig. 3 Mechanism of self-cleaning action of brous materials.

cotton by applying anatase titanium dioxide nano-colloid to cotton bers using the conventional dip-pad-cure process (Fig. 4). The ethanol-based nanocrystalline anatase colloid was nucleated from titanium tetraisopropoxide through a facile sol gel process.27,28,43 The principal reactions are shown below: Ti(OPr)4 + 4EtOH / Ti(OEt)4 + 4PrOH Ti(OPr)4 + H2O / Ti(OH)4 + 4PrOH Ti(OEt)4 + H2O / Ti(OH)4 + 4EtOH Ti(OH)4/TiO2 + 2H2O (7) (8) (9) (10)

Cotton bers were dipped in the as-prepared titanium dioxide nano-colloid and then pressed at a pressure of 2.75 kg cm2 at a roller rotation speed of 7.5 rpm. The pressed samples were dried for 10 min in a preheated oven at 80  C followed by curing at $100  C for 5 min. The anatase crystalline form was then induced by hydrothermally treating the bers in a boiling water bath for 3 h.27,44 The identication of the anatase characteristics on cotton surface using scanning electron microscopy (SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM) veried the success of anatase titanium dioxide

Recent developments of photocatalytic self-cleaning surface functionalization of brous materials

Denition of photocatalytic self-cleaning bers Photocatalytic self-cleaning bers are brous materials formed by imparting photocatalytic function through surface functionalization treatment, wherein the bers are able to clean themselves when exposed to light. The mechanism of the self-cleaning action of bers is shown in Fig. 3. Photocatalytic self-cleaning bers do not only possess self-cleaning property, but also antimicrobial, deodorizing and UV blocking functions. Self-cleaning cellulosic bers The concept of self-cleaning bers was rstly introduced by Daoud and Xin27 who successfully developed self-cleaning
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Fig. 4 Schematic diagram of dip-pad-cure surface coating.

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deposition on cellulosic materials with a strong anatase-cotton adhesion.27,28,43 The phase and size of crystallites are two major factors affecting the photoactivity and optoelectronic properties of titanium dioxide. By increasing the temperature and reaction time of the synthetic process to 60  C and 16 h, respectively, nanocrystalline single-phase anatase particles with a diameter of 5 nm were produced leading to a substantial improvement in the photoactivity.5,7 Using this approach, anatase could be grown on cellulose substrates without the need for the post-hydrothermal treatment.5,7 It was demonstrated that anatase-coated cotton has the ability to decompose organic contaminants, dirt and microorganisms when exposed to UV irradiation.5,7,27,43,44 Fig. 5 shows an example of the antimicrobial property of self-cleaning cotton in decomposing staphylococcus aureus. In addition, the photo-stability and UV protection of cotton were signicantly improved after coating due to the ability of titanium dioxide to absorb ultraviolet light.7 Dong et al. also tried to grow titanium dioxide nanoparticles on cotton fabrics for decomposition of gaseous airborne pollutant using polyglycolbased P-25 dispersion.8 The authors reported that the dosage of titanium dioxide dispersion affected the efciency of ammonia decomposition, where dyed cotton displayed similar results as undyed cotton.8 Over the past 5 years, various solgel synthesis conditions, such as temperature, reaction time, precursors and stabilizers, were adopted and modied to prepare titanium dioxide colloids for the formation of photocatalytic cellulose bers.4553 The synthesis conditions of these methods are summarized in Table 1. On the other hand, Zhang et al. successfully coated anatase on the cotton surface via microwave-assisted liquid phase deposition with hexauorotitanate ammonium ((NH4)2TiF6) as a precursor,9 where highly crystalline anatase was clearly evident on the cotton surface.9 The liquid phase deposition method received attention because of its simplicity in forming titanium dioxide on various substrates with a large surface area at low temperature which makes it also suitable for thermally sensitive substrates. The authors depicted that high photocatalytic activity and stable self-cleaning performance were achieved as evidenced by degradation of methylene blue within 3 h. Meanwhile, Kiwi et al. investigated the possibility of producing self-cleaning cellulosic bers by loading P-25 on cotton surface using nontoxic chemical spacers.10 The schematic diagram is shown in Fig. 6. The surface of cotton bers was activated by immersion in different spacer solutions including succinic acid,

Fig. 5 Antibacterial effect of self-cleaning cotton in decomposing staphylococcus aureus.

1,2,3-propanetricarboxylic, and 1,2,3,4-butanetetracarboxylic acid for 1 h. The dried bers were immersed into P-25 sonicated suspension at 75  C for 1 h, followed by 1 h drying at 100  C.10 The study demonstrated that, while no degradation of the ber surface was observed, the titanium dioxide-spacer-cotton was able to mineralize a variety of stains, including red wine, concentrated coffee, make-up solution and simulated human perspiration (a mixture of L-histidine-chloride, sodium chloride and sodium phosphate), through the photo-generated reactive species during the photocatalysis process.10 In general, the use of spacer showed success in incorporating titanium dioxide with cellulose materials; however, optimization of binding condition, such as spacer concentration and multilayer loading, was needed to achieve sufcient photocatalytic performance. In other contributions, Kiwi et al. incorporated the dipcoating method with different pre-treatment processes to produce highly functional self-cleaning cotton textiles.4850 With the aid of radio frequency (RF) plasma (vacuum/atmospheric), microwave (MV) plasma or vacuum/atmospheric UV irradiation surface activation pre-treatments, negatively charged functional groups (e.g. carboxylic, percarboxylic, epoxide and peroxide groups) could be introduced to the cotton surface through the formation or interaction of active/excited oxygen species (anionradical O, atomic O, singlet 1O2, cation-radical O+) to anchor titanium dioxide.45 The surface of bleached and mercerized cotton samples was activated differently depending on the type of systems used. Generally, the plasma approach (RF- and WV-plasma) introduces active oxygen species or ionized gas (atomic oxygen, positive or negative oxygen ions, excited oxygen radicals) on ber surfaces forming chelating groups for titanium dioxide binding, while the UV irradiation approach (vacuum and atmospheric) excites the upper layer of the cellulose bers using only atomic oxygen and excited oxygen species through UV light.48,50 After the surface activation pre-treatment, cotton bers were able to bind in titanium dioxide in both forms, powder suspension and colloidal solution. Comparing to the chemical spacer technique,10 UV pre-treated cotton demonstrated twofold improvement in decomposing red wine and coffee stains, signifying the prospective of using such technique in improving the adhesion of titanium dioxide to cotton.48 A more uniform titanium dioxide coating was obtained on UV pre-treated cotton than RF- and MV-plasma.48,50 When compared to hightemperature heat treatment or chemical/solvent-based surface modication, RF- and MV-plasma and UV irradiation pretreatments are environmentally friendly techniques, wherein the short treatment time and the absence of solvents reduce the energy and chemical consumption. However, the drawback of these systems is the requirement of immediate loading of titanium dioxide after pre-treatment due to the short life-time of the surface-generated reactive species. Doping titanium dioxide with other metals or metal oxides, such as Au/TiO2, SiO2/TiO2, is considered a potential strategy in making titanium dioxide on cellulose strongly photoactive with good reproducibility.5153 Few researchers proclaimed the use of SiO2/TiO2 colloid coating in boosting the photocatalytic efciency and its stability.51,52 There is a general agreement that SiO2/TiO2-coated cotton materials possess high photocatalytic performance and outperformed pure titanium dioxide coating, while maintaining cottons intrinsic property.
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Table 1 Summary of TiO2 solgel synthesis conditions for producing self-cleaning cellulose Precursor TIP TIP Medium Ethanol and water Ethanol Ethanol and water Water 2-Propanol HCl Ethanol and water Water Water Stabilizer Acetic acid Acetic acid and HNO3 HNO3 HNO3 Acetic acid and HNO3 HNO3 and acetic acid Synthesis condition Stirred at 40  C for 1 h Stirred at room temperature, pH 1 2 Stirred at 23, 38, or 58  C for 16 h Ultrasonic for 5 h, added polyglycol and stirred for 30 min Cooled in an ice bath and stirred for 1 h Cooled at 0  C in an ice bath Stirred at 25, 40, or 60  C for 16 h Stirred at 80  C for 30 min, mixed with SiO2 Ludox SM-30 in a 1 : 1 volume Stirred at 60  C for 16 h, pH 12 Ultrasonic SiO2 powder in TiO2 sol for 15 min, aged for 12 h to form coreshell structure, pH 35 Stirred for 6 h for peptization, autoclave heated for 3 h at 130  C, pH 0.7, 3, 7 Stirred for 23 min under argon gas ow Stirred for 30 min under argon gas ow Stirred for 30 min under argon gas ow Stirred for 45 min, pH 1.5, 2, 3.5, 4.5 Stirred at 80  C for 30 min, autoclave heated at 250  C for 12 h Phase Anatase Anatase Anatase Anatase rutile Rutile Rutile Anatase Anatase Anatase Reference 27 28 5 8 48 6 7 51 52

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TIP Degussa P-25 TIP TiCl4 TIP TIP TIP

TIP TIP TIP TIP Ti(OC4H9)4 TIP

Water 2-Isopropanol 2-Isopropanol and water Isopropanol Ethanol Water

HNO3 Triethyl amine HCl HCl HCl HNO3

Anatase rutile brookit Anatase Anatase Anatase Anatase

45 46 46 53 47 50

Although most of the research on self-cleaning cellulose was conducted on cotton, other cellulosic materials, such as wood, paper and bamboo bers, have also been investigated.15,5457 For instance, self-cleaning paper handsheets (wood cellulose bers) were produced by Marques et al.54 Wood bers (Eucalyptus globulus), composed of 85% cellulose and 15% glucuronoxylan, were mixed with titanyl oxysulfate (TiOSO4)/sulfuric acid solution at 100  C for 7 h using the controlled hydrolysis process. Titanium dioxide/cellulose composite bers were formed after drying at 50  C for 24 h. The handsheets were prepared by vacuum ltration and hot press according to ISO 5269/1.54 Although titanium dioxide was well retained in the cellulose bers, the bers exhibited photodegradation as demonstrated by the photo-yellowing effect after light exposure.54 Lately, the same research group reported an approach to overcome this limitation. Using tetraethoxysilane (TEOS), phenyltrimethoxysilane (PTMS) or trialkoxysilanes (OTMS) as a binder to form TiO2/ SiO2/cellulose nanocomposites can reduce the direct contact

between titanium dioxide and wood bers, resulting in protection of the bers with improved photo-stability.56 However, the complex procedures involved may not be practically favored. Self-cleaning protein bers Although intensive research has been conducted on cellulosic brous materials for exploring the potential application of titanium dioxide photocatalyst, little work has been reported on protein brous materials. The exploitation and development of such bers had largely been hampered due to their limited chemical, thermal and photo-stability.6,49,5865 In 2005, Kiwi and co-workers attempted to bind titanium dioxide with wool-polyamide blended fabrics.6,49 As opposed to cellulose, the surface chemical structure of keratin bers is irregular and the anchoring surface functional groups for titanium dioxide binding such as carboxylic and hydroxyl groups are less than 50% leading to ineffective photocatalytic property. After introducing a variable

Fig. 6 Schematic diagram of application of chemical spacers.

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density of negatively charged functional groups (COO, O O) using RF-plasma, MV-plasma or vacuum UV irradiation activation, the titanium dioxide particles could be attached on the modied wool-polyamide surface through electrostatic interaction with positively charged Ti4+.6,49 The modied woolpolyamide surface could work well with different titanium dioxide colloidal solutions. The experimental conditions of this method are summarized in Table 2. The research demonstrated that titanium dioxide loaded wool-polyamide blend possessed photocatalytic self-cleaning ability in decomposing dust, concentrated coffee and red wine stains with fair reproducibility after dry-cleaning.6,49 Although the self-cleaning wool-polyamide exhibited sound photocatalytic ability, plasma and UV irradiation-induced surface activation pre-treatment is expensive and difcult to implement at a large scale. Later on, Daoud et al. explored the possibility of extending the application of self-cleaning surface functionalization treatment to pure protein keratin-type wool bers using a modied titanium dioxide colloid and a wet surface modication approach.7,58 The solgel formulation was prepared by hydrolysis and condensation reactions of titanium tetraisopropoxide in acidic aqueous solution containing ethanol, acetic acid and hydrochloric acid. Acylation of wool bers with acid anhydride was introduced to enrich the bers surface with carboxyl groups, which enhanced the anatase coating and thus the self-cleaning functionality.58 In this approach, the wool bers were subjected to succinic anhydride solution in DMF at 65  C for 2 h for the succinylation reaction. The reactivity of the backbone chains of wool bers was enhanced through the introduction of additional carboxylic groups to keratins reactive sites such as carboxylic, hydroxyl, amino and thiol groups.58 The deposition of titanium dioxide on wool ber increased by two-fold as quantitatively evidenced by X-ray photoelectron spectroscopy (XPS). In later research, ethanol was replaced by water as a medium toward a more friendly process environmentally and industrially.59 Meanwhile, Hurren et al. investigated the photocatalytic reactivity of titanium dioxide-coated wool fabrics particularly in decomposing red wine stains.60 A titanium dioxide colloid was synthesized using titanium butoxide (Ti(OC3H9)4) in acidic aqueous medium containing hydrochloric acid and ethanol under an inert atmosphere of nitrogen for 2 h. Wool fabrics were dipped in the prepared solution for 30 s, followed by drying at 120  C for 1 min and curing at 60  C for 16 h. Hurren et al.

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revealed that while the UV absorption of titanium dioxidecoated wool was in positively proportional with red wine degradation, the titanium dioxide particle size on coated wool was inversely proportional to red wine degradation. More recently, further research was conducted by Daoud and co-workers, in which the synthesis condition of anatase colloid was modied in terms of acid stabilizers, synthesis time, photocatalyst concentration, and curing conditions, in order to optimize the photocatalytic efciency of self-cleaning keratins.59,61,62 Single-phase nanocrystalline anatase was successfully nucleated at 60  C within only 2 h of synthesis time.6164 Besides, the selfcleaning formulation preparation process was more compatible with industrial conditions. It was found that anatase-coated wool bers possessed good UV protection property and reproducible photocatalytic ability without the need for surface activation pretreatment.59,61,62 On top of this, the same research group explicated that the deterioration of the intrinsic physical and mechanical properties of wool bers after the titanium dioxide coating treatment could be substantially recovered with minimal adverse effect on the photocatalytic self-cleaning performance using a simple post-treatment with silicone.64 Self-cleaning keratins are currently in the stage of further development and optimization for potential commercialization. Self-cleaning synthetic bers The application of photocatalytic substances in pure synthetic bers, synthetic ber blends, and other brous polymers has also been investigated. In 2005, Kiwi et al. prepared rutile titanium dioxide colloid using the solgel process and a hydrothermal treatment at 100  C for 16 h. They developed self-cleaning polyester using different pre-treatments, such as RF-plasma, MW-plasma and vacuum-UV, to activate the ber surface and enhance the photocatalytic performance under visible light.6,49 Titanium dioxide has poor compatibility with synthetic bers, such as polyester and polyamide, due to the lack of anchoring functional groups. Following a similar approach, Qi et al. activated the polyester surface using a low temperature plasma treatment in an attempt to enhance the chemical bonding between titanium dioxide and polyester bers.65 Other potential self-cleaning brous materials had also been proposed by different research groups.12,6668 Yu et al. developed self-cleaning glass ber with stable photocatalytic activity and low

Table 2 Summary of TiO2 solgel synthesis conditions for producing self-cleaning wool-polyamide Precursor Degussa TiCl4 TIP TIP Medium Water Ice cold water (2  C) 2-Propanol 2-Propanol Stabilizer HCl HNO3 HNO3 Synthesis condition Sonicated at 60  C for 30 min Cooled at 0  C in an ice bath Cooled in an ice bath and stirred for 1 h Cooled in an ice bath and stirred for 1 h, autoclave at 100  C for 16 h for growing TiO2 particles, followed by stirring and sonication for dispersion Cooled in an ice bath and stirred for 1 h, autoclave at 220  C for 16 h for growing TiO2 particles, followed by stirring and sonication for dispersion Phase Anatase Rutile Rutile Rutile Grain size 3040 nm 57 nm 57 nm 1012 nm

TIP

2-Propanol

HNO3

2025 nm

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deactivation rate by a liquid phase deposition method, in which glass bers were immersed in TiF4 and H3BO3 mixture at 60  C for 12 h followed by calcination at 300  C for 2 h.12 In this method, anatase titanium dioxide with a particle size of 20 70 nm could be uniformly and dispersedly deposited on glass ber surfaces.12 Concurrently, Jia et al. successfully loaded commercially available P-25 on activated carbon bers (ACF) by a dip coating treatment followed by calcination at 300  C for 2 h under ambient pressure.66 Later on, a new soft process method using microwave irradiation was used for depositing titanium dioxide on polyvinyl alcohol (PVA) bers at low temperature. Tetrabutyl orthotitanate was hydrolyzed with tetrabutyl ammonium hydroxide forming titanium dioxide colloid, followed by 2 h reuxing for crystallization. The work concluded that the titanium dioxide-coated PVA not only possessed high photocatalytic ability in decomposing methylene blue, but also demonstrated good antimicrobial effect in sterilizing both Gramnegative (Escherichia coli, Pseudomonas aeruginosa) and Grampositive bacteria (Staphylococcus aureus) under UV irradiation.67 On the other hand, new approaches toward self-cleaning brous materials were suggested. Instead of coating titanium dioxide particles on the substrates surface, bers were incorporated with titanium dioxide forming titanium dioxide-ber composites.6971 Wei et al. developed titanium dioxidepolypropylene nanocomposite bers, wherein P-25 nanoparticles were mixed with polypropylene granules powder through tumbler mixer for 30 min, followed by extrusion from pilot-plant scale melt-extrusion equipment through melt-compounding under heat treatment at 230  C.69 The nanocomposite bers were found to contain titanium dioxide but the titanium dioxide coverage on polypropylene ber surface was poor due to the extensive aggregation of titanium dioxide particles. Moreover, the photoactivity of such bers could not be established as the work lacked quantication of the photocatalytic activity.69 Alternatively, a two-steps synthesis was employed by Zhang et al. in producing titanium dioxide bers according to Fig. 7.70 More recently, Im et al. attempted to integrate co-doping in titanium dioxide nanocomposite bers for improving the photodegradation properties under solar light. Carbon, nitrogen, boron and uorine were co-doped with anatase titanium dioxide and electrospun with PVA forming visible-light active hydrogel bers.71 However, compared to the surface coating approach, production of titanium dioxide nanocomposite bers appears rather complex and needs further investigation. Due to the concurrent signicant impetus for further research and development in this area, it is expected that these efforts may lead to a wide range of applications to include more exible organic materials in the foreseeable future.

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Fig. 7 Two step synthesis method in producing TiO2 bers.

reaction,3,4 which is capable of removing unpleasant smell such as perspiration, shoe odor, vehicle smoke, cigarette smoke, and organic stains, such as coffee, red wine and oil, that cannot be effectively cleaned by laundry or dry-cleaning.3,4,6,7,37 Moreover, bers such as wool and silk are more liable to attack by microorganisms. Titanium dioxide can decompose the mold spores adhered on the ber surface using similar mechanism as antifouling and deodorizing.3,4,37 Therefore, brous materials with titanium dioxide surface coating can act as a protective layer to prevent the growth of mold spores on bers. On the other hand, delicate clothing, such as chiffon and satin, easily suffers from distortion, dimension change and pilling effect through the washing process, which affect their appearance, properties and general functions. Since the self-cleaning function is triggered by simply exposure to light, washing-induced damage or dimension distortion of clothing can be avoided due to the reduction of wash cycle, contributing to the extension of the life-time of such materials. Resources saving and cost effectiveness. Self-cleaning brous materials can be viewed as one of the solutions to concurrent energy and resources crisis. Because clothing or apparels equipped with auto-cleaning property not only offer the aesthetic advantage by maintaining its cleanliness, but also appreciably cut the cost of cleaning and maintenance through reducing the use of chemical detergents and frequency of recurring washing. Moreover, time and power consumption required for the laundry process can also be economized. Self-cleaning brous materials provide economic and environmental benets to our society. Protective clothing UV protection. Ultraviolet radiation is divided into three categories according to its wavelength: UV-A (400320 nm), UV-B (320280 nm), and UV-C (280100 nm). Owing to air pollution, the depletion of ozone layer allowed harmful UV radiation to pass through the Earths atmosphere and cause a signicant increase in the UV intensity in the atmosphere. Overdose of UV radiation can result in chronic reactions and
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Functions of photocatalytic self-cleaning bers and application thereof

Self-cleaning daily apparels Anti-fouling, anti-odor and anti-mold. Fibrous materials structures get dirty and smelly easily, therefore frequent washing is necessary for maintaining cleanness. Researchers reported that the titanium dioxide-coated surface has an excellent soil resistance and deodorizing properties due to its strong oxidation
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skin damages such as sunburn, acceleration of premature skin ageing, promotion of photo-dermatosis, genetic (i.e. DNA) damage, and skin cancer.72 Therefore, in the prevention of life threatening skin cancers, efforts are being dedicated to produce sun protective clothing in order to enhance the skin protection against excessive biologically harmful UV radiation, primarily UV-B due to its high skin damage potential.72 Fibrous materials, such as polyester, wool and silk, naturally absorb UV rays due to the presence of aromatic groups in their structure; however, bers like cotton and polyamide are permeable to the UV radiation.73 Regardless of the ber type, the change of fabric weight, color, structure, porosity and elasticity are also factors that can undermine the UV absorption or scattering efciency of brous materials. Titanium dioxide-coated self-cleaning bers can be a good alternative to maintain the UV protection efciency. As a non-toxic inorganic UV absorber, titanium dioxide is favorable for UV protection due to its chemical and thermal stability.74 Forming a thin transparent layer of nanocrystalline titanium dioxide on the fabric surface can provide excellent UV blocking effect and enhance the skin protection of clothing against harmful UV light, particularly for infant/children wear, summer clothing, and apparels for outdoor occupations. These UV-shielding brous materials can also be used in external structural applications such as awnings, sunshades, blinds and related applications. Medical protection. Surgical operation has to be carried out under sterile condition to avoid the chances of infection. Medical fabrics, such as operation gown, hospital patient gown, surgical gloves, mask, surgical cap, must be free from germs. With a titanium dioxide coating, the cleanliness of these brous materials can be maintained due to their anti-bacterial property suppressing the growth of the bacteria on the substrates surface. The chances of infection can be substantially reduced due to the reduction of viable bacteria, germs or virus during surgery. Cancer is the rst disease causing large population of human death. Fujishima et al. applied photocatalyst particles to control the growth of cancer T24.75 In animal experiments and testing, photocatalysis can effectively reduce the affected area through inserting a photocatalyst into the infected cancer area with a UVoptic cable triggering the reactivity.75 It is anticipated that the application can be extended to medical healing fabrics. Instead of using titanium dioxide nanoparticles, photocatalytic medical healing fabrics can be placed in the infected areas for controlling the growth of cancer cells. Thus, the possibility of individual nanoparticles penetrating into the blood stream and damaging human tissue can be avoided. Household appliances and interior furnishing materials Antimicrobial and dustproof. The photocatalytic self-cleaning surface has now emerged in household products such as kitchen cloths, bath towels, furniture. Traditionally, chemical agents such as bleaching agent and alcohols are used for cleaning and disinfection purposes. However, inhalation of or contact with those chemicals could be harmful to human body. Besides, these agents only provide a short-term effect leading to the need of persistent application. Alternatively, self-cleaning brous materials can achieve long-term dustproof and anti-bacterial
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functions. With the use of low intensity light irradiation, nanosized titanium dioxide-coated self-cleaning bers can oxidize surface-adsorbed organic contaminant, and provide effective protection against dust, bacteria and disease-causing microorganisms.4 On the other hand in existing antimicrobial products, the antimicrobial agents leach from the surface to kill microorganism on contact. If this type of antimicrobial agents is applied to fabrics that are in contact with skin, the agents may cross the skin barrier causing allergic reactions and rashes, or even kill useful organisms.72 Furthermore, since these agents are mobile, microorganisms have the opportunity to adapt and become resistant rendering them ineffective. However, titanium dioxidebased coating would not leach from the surface; the generated active radicals only decompose the microorganisms that come in contact with the surface of titanium dioxide. Moreover, selfcleaning bers cause no harmful effect to the dermis layer since the outermost layer (stratum corneum) of human skin can protect it from absorbing the active oxidizing substances produced from titanium dioxide.76 Since the self-cleaning surface is immobilized, most of the limitations of the leaching-type antimicrobial agents can be overcome.72 A hygienic living environment is a promise for a healthier and more sustainable life, particularly for children and the elderly. Air purication facilities. Air pollution, whether outdoor or indoor, is always a serious problem, which is directly affecting the living quality of all living organisms. Outdoor air pollution is due to the emission of air pollutants, for instance, nitrogen oxides (NOx), sulfur oxides (SOx), volatile organic compounds (VOC), and ozone (O3) from motors, power plants, and industries into the atmosphere, while indoor air pollution mainly comes from odor or toxic gases from daily life activity, such as the release of formaldehyde from renovation/construction or nitric monoxide from cigarette smoke. Air lters are air purifying devices, which mainly apply to building ventilation systems (smokestack, air conditioner, and stovepipe) and engines (motors). Incorporating titanium dioxide into cotton or pleated paper air lters can purify air from airborne organic contaminant. Installation of self-cleaning air lters at the opening of smokestacks and engines can eliminate the emission of harmful gases to the atmosphere; while air purier and air conditioner with self-cleaning air lters can maintain the indoor air quality reducing the occurrence of airinduced allergies such as sick building syndrome (SBS) or nasal allergy.

Limitations
Environmental concerns Although nano-sized titanium dioxide offers numerous benets, there is also potential for adverse consequences related to public health and environment. In view of the increasing demand on photocatalytic self-cleaning brous products, health and environmental concerns in the production and use of nano-structured titanium dioxide surface coating have been raised. Due to the lack of comprehensive studies on the potential risks of nanocrystalline titanium dioxide-coated brous materials, many
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scientists worried about the possible effects on human and the environment. One of the concerns is the risk of exposure during manufacture and application. The generation of waste chemical residues or wastewater during the production of self-cleaning brous materials or possible leaching/peeling off of titanium dioxide nanoparticles from the ber surface during washing could lead to contamination of wastewater streams. On the other hand, exposure risks during the end of life disposal would also be of concern. In the event that such materials become widely used, improper disposal of nanomaterials could lead to a large amount of nano-sized titanium dioxide entering the soil. Tomson investigated the possibility of the transfer of nanoparticles to natural environment, and found that nanoparticles can travel through and store into soil.77 Earthworms can absorb nanoparticles from the contaminated soil and move up to the food chain. The research displayed a high possibility that nanoparticles would accumulate in the oceans, soil, plants and living organisms, and ultimately affecting the whole planet. Yet, little is known about the impacts of nanomaterials on the environment, and the potential risks of releasing nanoparticles into the environment might be underestimated. Potential risk and human safety concerns The lethal dose (LD50) represents the short-term poisoning potential (acute toxicity) of a substance, measured by the amount of a given substance, given all at once that causes the death of 50% of a group of test animals. Toxicologists reported that the LD50 value of titanium dioxide for rat is above 12 g kg1 after oral administration.78 Epidemiologists also reported that no carcinogenic effect and nonmalignant respiratory disease for human were observed.79 The studies demonstrated neither signicant absorption nor organ storage due to the ingestion of titanium dioxide, suggesting that titanium dioxide has low toxicity.78,79 Therefore, scientists in general, assume the use of titanium dioxide is safe. However, titanium dioxide at the nanoscale behaves differently when compared to its bulk counterpart. It is proven that particles at the nano-scale are toxic to mice lung, indicating the potential to cause similar allergies to human body.80 It is of concern if individual titanium dioxide nanoparticles that may peel off a ber coating could then be inhaled or penetrated through human skin to blood stream. The titanium dioxide nanoparticles might accumulate in the body causing toxic effects such as allergy or inammation to lungs or other organs. Although some researchers claimed that titanium dioxide nanoparticles are permanently bonded to the brous materials,7,10,59,65 there is no testing standard for proving the safety exposure level regarding the release of titanium dioxide nanoparticles from such coatings. This should also be addressed in the further research of photocatalytic self-cleaning brous materials. Photocatalytic efciency and stability Factors such as substrate selection, dispersion technique and light source affect the photocatalytic self-cleaning property and its stability. For some bers, the attachment of titanium dioxide on the ber surface is weak because of the insignicant amount and random distribution of anchoring functional groups on the ber surface. Inadequate and uneven photocatalytically active
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sites may undermine the efciency and reproducibility. Although calcination and high temperature curing are common posttreatment techniques for improving the crystallization and bondability of titanium dioxide, these methods are not suitable for low thermally resistant brous materials. Low-temperature surface coating techniques have to be used when producing selfcleaning bers, which brings about difculty in acquiring stable photoactivity. Therefore, advanced synthesis and dispersion technologies have to be devised in order to acquire highly crystalline titanium dioxide to endure maximum photocatalytic effect and offset the constraints. Photocatalytic efciency depends on the branching of the reactive electron/hole pairs into interfacial charge-transfer reactions. Considering the structure of titanium dioxide, the large photonic band gap (3.2 eV in anatase form) limits the photoactivity to a specic excitation source within the UV range.3,4 Moreover, the recombination of the generated electronhole pairs by a rapid charge-transfer process and low interfacial charge-transfer rates decelerate the redox reaction.3,4 Another limitation of these bers stems from their passive approach. Although the photogenerated radicals on the titanium dioxidecoated surface may be able to diffuse as far as 20 mm from their microdomins,81 titanium dioxide does not take the initiative to capture all types of contaminants. Since organic contaminants or microorganisms must be adsorbed or come in contact with the self-cleaning surface microzones in order to trigger the decomposition process, this may hinder the photocatalytic efciency. Several research groups provided evidence that the photocatalytic efciency of self-cleaning brous materials decreased with repetitive washing or cycling application.6,12,4345,47 This could be attributed to weak titanium dioxide-bers bonding,28,4346 and/or reduction of active sites of titanium dioxide.12 Photocatalytic stability is determined by the amount of active titanium dioxide particles remaining on the ber surface over time. The lack of anchoring groups for titanium dioxide can result a temporary physical bonding rather than permanent chemical bonding,45,46 leading to short-term photocatalytic stability. In addition, the photogenerated oxidation and reduction sites on titanium dioxide surface may be occupied by the contaminants or byproduct generated during the photocatalysis process,12 causing deactivation of photocatalytic active sites and affecting the stability of the selfcleaning function. Although researchers proclaimed that the deceleration of photocatalysis was within an acceptable range,6,12,28,4345,47,66 no standard measurement is available for verication. Another concern is that the photocatalytic efciency and stability of self-cleaning brous materials are mainly evaluated by contaminants removal and antimicrobial tests,511,1315,2732,4371 which are usually carried out under short-term exposure conditions (<100 h). Such exposure duration may not be long enough for selfcleaning bers to demonstrate their real stability. It should also be considered to have long-term stability analyses according to the target application.

Future prospects
Visible light-driven photocatalysts Although numerous research studies have been conducted to maximize the photocatalytic performance, many factors that
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signicantly inuence the efciency of photocatalysts, are yet to receive comprehensive investigation. One of the vital concerns is the limitation of the light absorbability. Current photocatalysts inherently require ultraviolet light irradiation to trigger the advanced oxidation effect. Therefore, the effectiveness of the photocatalytic activity is highly dependent on the UV intensity of incident light. However, the fear of overexposure to healthdamaging ultraviolet light is a major concern. Moreover, ultraviolet light constitutes only 0.1% of indoor lighting, which may substantially limit the efciency of the photocatalytic selfcleaning effect in indoor applications. Therefore, it is essential to widen the effective absorption wavelength range of the photocatalyst to include other regions such as visible light or even infrared for improving the usability of the photocatalysts. Remote photocatalytic effect The possibility of remote photodegradation by titanium dioxide was raised by Haick and Paz,81 who suggested that the photogenerated oxidizing active species (e.g. hydroxyl radicals, superoxide anions, singlet oxygen, hydrogen peroxide) could diffuse from the surface of irradiated titanium dioxide to mineralize distant contaminants at very short times.81 Although this nding contradicts the general belief of LangmuirHinshelwood kinetics82 that hydroxyl radicals are immobile and the adsorption of contaminant on the surface of photocatalysts is a precondition for photocatalysis,82 the authors presented a new insight in photocatalytic mechanism, that may account for the photoactivity in the vicinity of photocatalysts. Yet, knowledge of such concept is limited. Uncertainties remain regarding the diffusion rate of active species and the stability of such surface migration. Modication of application process The methods of preparation of photocatalysts and their application to brous materials are important factors in improving the photocatalytic performance and stability. Uneven distribution of the photocatalyst and non-sustainable coating are common problems encountered. These factors may impact on the efciency and long-term stability of the photocatalytic self-cleaning function. Thus, further investigation is recommended to advance the self-cleaning surface coating process such as through the incorporation of surface activation pre-treatment or post-treatment processes, so as to develop an optimum application sequence to boost the efciency and stability of the photoactivity. Empirical measurement methods Photocatalytic self-cleaning brous materials have been witnessing accelerated technological progress in recent years. However, up till now, there has been no recognized international specication in standardizing the testing of efciency and safety of these materials. Considering the potential of such materials and their wide applications, there is a pressing need to establish a series of universal empirical testing standards for objectively characterizing and evaluating the performance of newly developed self-cleaning brous products. In terms of safety, government regulation and labeling requirements for the production
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and use of nanocrystalline titanium dioxide-functionalized selfcleaning brous materials are also necessary.

Conclusions
In this contribution, an overview of the development of photocatalytic self-cleaning bers and their future prospects is presented. These bers with their tremendous potential in a wide range of applications may bring about substantial benets to mankind and the environment through the saving of natural resources consumed during washing and cleaning processes. Although more research is needed to ensure maximum efciency of the technology at minimum impact on the safety of living organisms and the environment, the scope of this technology may also be extended to as yet unknown elds.

Acknowledgements
The authors gratefully acknowledge Monash Research Graduate School (MRGS) and School of Applied Sciences and Engineering at Monash University for their nancial supports in this study.

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