Environ Sci Pollut Res DOI 10.

1007/s11356-013-1600-6

RESEARCH ARTICLE

Immobilized Fe (III)-doped titanium dioxide for photodegradation of dissolved organic compounds in water
Isaac W. Mwangi & J. Catherine Ngila & Patrick Ndungu & Titus A. M. Msagati & Joseph N. Kamau

Received: 1 November 2012 / Accepted: 25 February 2013 # Springer-Verlag Berlin Heidelberg 2013

Abstract Photocatalytic degradation of dissolved organic carbon (DOC) by utilizing Fe(III)-doped TiO2 at the visible radiation range is hereby reported. The photocatalyst was immobilized on sintered glass frits with the coating done by wet method, calcinated at 500 C and then applied in a photodegradation reactor. The addition of a transition metal dopant, Fe(III), initiated the red shift which was confirmed by UVVis spectroscopy, and the photocatalyst was activated by visible radiation. X-ray diffraction patterns showed that Fe(III) doping had an effect on the crystallinity of the photocatalysts. Mixtures of DOC and associated coloured solutions were degraded in first-order kinetics, showing that the degradation process was not dependent on intermediates or other species in solution. A reactor with a catalyst coating area of 12.57 cm2 was able to degrade 0.623 mg of the dissolved material per minute. Exposure of the reactor to hostile acidic conditions and repeated use did not compromise its efficiency. It was observed that the reactor regenerates itself in the presence of visible light, and therefore, it can be re-used for more than 100 runs before the performance dropped to <95 %. The results obtained indicate that the photocatalyst reactor has a great potential of application

for use in tandem with biosorbent cartridges to complement water purification methods for domestic consumption. Keywords Immobilized photocatalyst . Doped titanium dioxide . Dissolved organic compounds . Photodegradation . Spectrophotometric red shift . Kinetics

Introduction The presence of dissolved organic matter derived from pharmaceutical, natural or synthetic sources is an emerging water pollutant that is of concern to hydrogeologists and environmental scientists. Dissolved organics pose a problem because they provide a carbon source for bacterial growth, generate odour and cause biofouling on the surface of items used. They are not easily removed in biological wastewater treatment process; thus, there is a need for a treatment process to remove these contaminants from natural and wastewaters (Kochanyt and Bolton 1992). Several methods have been employed for removal of dissolved organic carbon (DOCs) in water which include adsorption, membrane filtration, cloud point extraction, solvent extraction, co-precipitation, chemical oxidation and complexation with some specific metal ions (Yldz et al. 2011). It has been reported that some of the complex compounds formed are more toxic in nature than the DOCs themselves; hence, such complex formation methods are not appropriate (Ekpete and Horsfall 2011). Among these techniques, solid phase extraction (SPE) which uses of a sorbent that retains the analyte is the most attractive (Chen et al. 2009). SPE is a simple 78technique with numerous advantages as several analytes can be enriched and separated simultaneously (Chen et al. 2009). The SPE material should possess qualities such as high surface area, high purity and good sorption properties including porosity, durability and uniform pore

Responsible editor: Philippe Garrigues I. W. Mwangi : J. C. Ngila (*) : T. A. M. Msagati : J. N. Kamau Department of Applied Chemistry, University of Johannesburg, Doornfontein Campus, Doornfontein, P.O Box 17011, 2028, Johannesburg, South Africa e-mail: jcngila@uj.ac.za P. Ndungu School of Chemistry & Physics, University of KwaZulu-Natal, Westville, P/Bag X45001, Durban 4000, South Africa I. W. Mwangi Chemistry Department, Kenyatta University, P.O Box 43844, Nairobi 00100, Kenya

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distribution. Adsorption through the use of functionalized adsorbents such as activated carbon has been the most applied treatment processes. It had been regarded as one of the best available environmental control technologies used to trap the DOCs. However, the disadvantage of such methodology is generation of spent adsorbents which thereafter become contaminant of concern due to the need of further disposal problem (Agrawal and Sahu 2006). The limitation of the above methods has led to the consideration of other approaches such as photodegradation not associated with generation of contaminants. This technique has been found to be suitable not only for the treatment of wastewater but also as an alternative to conventional drinking water treatment method as well as for the production of ultrapure water for pharmaceutical applications (Huang et al. 2000). Advanced Oxidation Processes have been reported to be useful for heterogeneous photooxidation of organic pollutants in wastewater (Maldonado et al. 2007). Application of TiO2 as a photocatalyst has shown great ability to destroy a wide range of organic pollutants at ambient temperature and pressure, without generation of harmful by-products (Bhatkhande et al. 2002; Hoffmann et al. 1995; Gupta et al. 2006, 2007a, b, c; 2010). The catalyst is usually suspended in the solution provided that there is a contact between the photocatalyst and dissolved impurities. As photocatalysis is a surface phenomenon, the remediation process of a given pollutant allows one to predict the mechanism and kinetics that promote the pollutants photooxidation (Valente et al. 2006). However, efforts to have the degrading agents immobilised on a convenient support have been difficult for practical applications. In some cases, applied support materials themselves have been found to undergo the photocatalytic degradation process hence presenting a challenge (Grzechulska-Damszel 2009). Moreover, the choice of the support plays a major role in the stability and photocatalytic properties of the adsorbent. The surface behaviour of TiO2 is of great interest because of its ability to catalyze the photooxidation and subsequent degradation of organic molecules. It can be used for environmental remediation, where toxic materials at low concentrations are photocatalytically converted to harmless oxidation products such as CO2 and H2O (Thompson and Yates 2005). When TiO2 is illuminated with UV radiation, electrons on the surface are activated and fly off leaving electron-deficient holes as shown in Eq. 1. h n TiO2 ! e h 1

TiO2 (Thompson and Yates 2005). This mechanism can be explained by Eqs. 2, 3, 4 and 5 (Liu et al. 2007). h OH ! OH * h H 2O ! OH H h Pads ! P ads OH * Pads ! Poxd ! H 2 O CO2 2 3 4 5

where Pads represents the organic pollutants; Poxd is the oxidised organic pollutant and h+ is proton (hole). The aim of the present study is to develop a technology to degrade organic compounds in water using a reactor with a reusable TiO2 photocatalyst immobilised on a solid substrate. The catalyst was supported on sintered glass material number 3 pore size. The advantage of the support material is that, it forms strong surface bonds with the catalyst. Its porosity allows the TiO2 gel to easily pack itself freely within its structure and also allows the polluted water to flow freely through the pores (Hidalgo et al. 2004). Our study investigated the immobilization of Fe(III)-doped titanium dioxide photocatalytic material and its subsequent application for the degradation of DOC in water as a green remediation method for organic matter-polluted waters. The study also offers a UVVis spectrophotometric technique for determination of starch. The determination method is based on the coloured complex formed when iodine reacts with starch (Shi et al. (2009). The kinetics of the photocatalytic degradation of multi-component dissolved organics mixtures was also investigated with a view to understand the mechanism of degrading mixed components compared to the respective individual components. The findings may offer possible pathway for the degradation of each component in the DOC mixture.

Material and methods Chemicals and reagents All the solutions were prepared in double distilled water, and all the chemicals and reagents used were of analytical grade. The titanium oxysulphate (TiOSO4), potassium iodide, ferric nitrate, iodine, sodium acetate and hydrochloric acid (32 %) were supplied by Sigma Aldrich (Gauteng-Johannesburg, South Africa). Anhydrous starch for biochemistry and sodium hydroxide were supplied by Merck (Gauteng-Johannesburg, South Africa). Barium sulphate was supplied by Wako Pure Chemical Industries, Ltd, (Tokyo, Japan).

These discharged electrons have strong deoxidization ability, and will produce oxidation anion free radicals (superoxide species O-2) and oxyhydrogen free radicals (OH*) after reacting with H2O and O2 in solution. The excited O2- acts as an oxidizing agent for organic molecules on the surface of the

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Instrumentation Optical measurements were carried out at the appropriate wavelength on a Perkin Elmer LAMBDA 35 UVVis spectrophotometer (Massachusetts, USA). The solgel nanoparticles were sonicated using a Jeken sonicator; model PS-08A 1.3 L (Guangdong, China). Characterization of the photocatalyst was carried out on a Shimadzu UV-2450 (Tokyo, Japan) UV Vis spectrophotometer at its normal wavelength range (190 1,100 nm) while coupled with an integrating spheres assembly. The crystalline structure of the photocatalyst was studied by recording X-ray diffraction patterns of powdered samples of both the doped and original TiO2 material using a Rigaku Ultima ICV X-ray diffraction refractometer (Kyoto, Japan). Preparation of photocatalytic TiO2 coatings The TiO2 photocatalyst gel was prepared through hydrolysis of TiOSO4 with a dilute solution of 5 % NaOH (Hidalgo et al. 2004). This was done by adding 12.3 g of TiOSO4 in 100 mL distilled water resulting to a gel containing 4 % TiO2. The mixtures were stirred at room temperature, and then heated up to 85 C until a clear solution was obtained. To this solution, 20 mL of 0.1 M Fe(NO3)3 was added followed by a slow addition of 10 mL of 5 % NaOH solution until pH 5.5 was attained resulting in the formation of a gel. (Sonawane et al. 2004) The gel was continuously stirred and the temperature maintained for 6 h thereafter filtered and washed thoroughly. It was then re-suspended in distilled water (200 mL) and the product sonicated for 6 h. The resulting material was ready for immobilization on the sintered glass frits. The material was stored at 5 C when not in use. Coating was done on clean dried circular sintered glass frits with a diameter of 40 mm and a surface area of 12.57 cm2. The coating process which involved dipping the disks for 15 s and then withdrawn at a rate that ensured that the coating covered the substrate well (Fretwell and Douglas 2001). The disks were then dried at 110 C for 2 h and later calcinated at 500 C for 1 h, at a heating rate of 5 Cmin1 before being used for the photooxidation process. Characterization of the photocatalytic material was done with an integrated coupled assembly of a UVVis spectrophotometer. The sample was prepared by taking 2.0 mL of the sol gel and mixing it with 4.0 g of barium sulphate to make a thick paste. The mixture was then placed on the sample holder for analysis. Preparation of starch and iodine solutions A Standard iodine solution, 0.05 molL1 was prepared and stored in a dark environment. Standard starch stock solution was prepared by dissolving 0.1 g of soluble starch in 1 L of water to make 0.01 % starch solution. From this stock solution, subsequent dilutions were made.

Characterization of the photocatalyst Structural characterization using XRD The photocatalysts were characterised by recording diffraction patterns using NiK radiations. The instrumental setting had a copper radiation tube emitting a radiation of 0.15405 nm in 2 range from 15 to 60 at a scan speed of 0.2s1. The XRD peaks of crystal plane 101 for anatase usually appeared at 25.3 (2) and 110 at 27.4 (2) for rutile. XRD characterization was therefore carried out to establish if the chemical attachment of the Fe(III) dopant on the photocatalyst had happened or if there was transformation from anatase to rutile state. Optical characterization using UVVis spectrophotometry The photocatalyst coating material was characterised by UVVis using Ba2SO4 as the reference. Measurements were performed by placing the sample in front of the incident light window, and concentrating the light reflected from the sample on to the detector using a sphere with a barium sulfate-coated surface. The mechanism involves measuring the relative reflectance based on the coated barium sulfate. Photo remediation experiments The photocatalytic activity of the TiO2 coatings was tested by investigation of photooxidation of 0.01 % starch solution. The degradation of starch was then monitored using iodine solution as an indicator through the formation of a blue-coloured starchiodine complex (SI3) in the mixed solution (Shi et al. 2009). The procedure involved introducing the starch solution in the reactor and the photodegradation process observed by withdrawing 5-mL aliquots of the solutions at regular time intervals. Equal volumes of iodine solution were added to the aliquots and the final volume made to 100 mL with distilled water. Spectrophotometric measurements were then performed on the coloured solutions using a Perkin Elmer LAMBDA 35 UVVis spectrophotometer in the range 190900 nm. Effect of pH on degradation The effect of pH on the equilibrium constant was investigated by buffering the test solutions to pH values ranging between 3 and 12 and the above procedure repeated. Photo remediation experimental setup A schematic diagram of the reaction system is shown in Fig. 1. The photodegradation reactor consisted of a peristaltic pump set at a flow rate of 5.0 mLmin1 that homogenised the sample

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Phase characterization using XRD The results of the X-ray diffraction patterns of the TiO2 and Fe(III)-doped TiO2 photocatalysts are presented in Fig. 2. The results show a major crystalline peak in the TiO2 material (Fig. 2a) at 2 =25.22 and 37.79 indicating that the major phase present was the anatase form (Balasubramanian et al. 2003; Laokiat et al. 2012). The diffraction patterns of the Fe/TiO2 sample (Fig. 2b) show a low intensity XRD peak of iron at 2 =45.47. This may be because of a homogeneous dispersion of iron deposits on the nanoscale on the surface of the TiO2 photocatalyst. A similar peak was observed by Steiner et al. (2007) as they doped carbon nanotubes with Fe(NO3)3. The presence of a small peak at 2 =30.74 corresponded to the brookite phase (Laokiat et al. 2012). The two spectra of diffraction patterns show the difference between the TiO2 and Fe-TiO2-doped phases. Optical characterization using UVVis spectrophotometer The results from UVVis characterization of the photocatalyst before and after doping are presented in Fig. 3. Results in Fig. 3 show that absorption by pure TiO2 material (curve A) starts at 340 nm (UV region), while that by the Fe(III)-doped TiO2 material showed the absorption to start at 570 nm (visible region). The wavelengths of maximum absorption (max) for the two materials were found to be 261 and 330 nm,

Fig. 1 A setup of the photodegradation reactor

in the reactor, making sure that the species generated from the photocatalyst were well distributed for the degradation process. An aeration pump maintained a constant supply of oxygen to both the sample mixture and the surface of the photocatalyst.

Results and discussions Characterization The following techniques used for characterization are discussed under XRD, UVVis and chemical kinetics.
Fig. 2 XRD patterns of photocatalyst a TiO2 and b Fe(III) doped

Environ Sci Pollut Res Fig. 3 UVVis absorption spectra of thin films of A TiO2 and B Fe(III)-doped TiO2

respectively. The shift in the max observed in this study from low to higher wavelengths as shown in spectra A and B indicates a red shift as reported by Li et al. (2003). The red shift implies that the doping process enabled the photocatalyst to be excited by radiation in the visible light region. This confirms that Fe(III) doping of TiO2 affected its band gap when stimulated of visible light to excite electrons in the host material (Fig. 3). This can be explained by the fact that doping suppresses enhancement of electron-hole recombination and also generates catalytic sites on the TiO2 surface that serve to store electrons for subsequent transfer to acceptor species in the solution (Sonawane et al. 2004). Studies by Li et al. (2003) and Sonawane et al. (2004) reported that after using the doping, there is an increase in photocatalytic activity due to the shift in optical absorption, thus facilitating excitation by both UV (full range) and a portion of the visible range. Photodegradation of leached DOCs In our previous study, Mwangi et al. (2012), we reported that when maize tassels powder was used as a sorbent, it leached DOC in to the treated water, a phenomenon referred to as secondary pollution. A solution from the modified maize tassels was prepared (as explained in the previous study) and used for the current study. The solution (200 ml) was introduced into the photodegradation reactor and the remediation process monitored by withdrawing 5-ml

aliquots of the solutions at regular time intervals. To these aliquots, 5 ml of iodine solution was added and the final volume made up to 100 ml with distilled water. This produced a blue-coloured solution similar to observations made by Chance et al. (2010) where they carried out studies on spectrophotometric analysis based on starchiodine reaction. They observed several absorption peaks at 471, 350 and 280 nm. They assigned the peak at 471 nm to excess molecular iodine, while those at 350 and 280 nm were attributed to the iodate ion from the starchiodide complex (SI3) in the mixed solution. In this study, the samples in the reactor were kept under continuous agitation whilst natural light irradiated. The solutions were analysed on a UVVis spectrophotometer, and the results obtained are shown in Fig. 4. The results in Fig. 4 show the peaks at 350 and 280 nm which are due to the formation of I3starch complex (SI3). The concentration of the respective chromophores decreased with increase in degradation time. The observed absorption at 590650 nm is due to chlorophyll moieties in the maize tassels material (Wang et al. 2007). It was observed that the absorption by the chlorophyll species also decreased with increase in the photodegradation process. The decrease in intensity of the chlorophyll colour confirms that the photocatalyst eradicated the leached DOC colouration from the solution of the maize tassel. Thus, photodegradation process is effective in the removal of secondary pollution.

Environ Sci Pollut Res Fig. 4 Results of photoremediation of DOC obtained by leaching maize tassels: Degradation time periods in minutes for A =0, B =70 and C =190

Effect of pH on degradation The effect of pH on the degradation was investigated by buffering the test solutions at pH values ranging from 3 to 12. Each of the respective solutions (200 ml) was introduced into the photodegradation reactor and the extent of degradation monitored spectrophotometrically. The results obtained are presented in Fig. 5. The results show randomly overlaid spectra unlike the orderly overlaid pattern of the spectra previously observed in Fig. 4 when the solution was buffered at a single pH value. This could be due to the reactions between the DOC and buffering agents resulting in chromophores that absorb UV Vis radiation at the observed values. The oxygen species is the main agent for the degradation of DOC in the remediation process (Wang et al. 2007). However, the hole (h+), reacts with water molecule to produce hydroxide ions (OH) creating an alkaline environment which suppresses the formation of this free radical. In a normal photooxidation process, the electron (e) reacts with dissolved O2, to produce a superoxide, O2, species (Sonawane et al. 2004). Studies by Stamatovska et al.

(2006) reported that change in frequency of maximum absorption, max (solvatochromic effect), of same chromophores was caused by different pH environments. They had observed that high acidic environments cause the shift of absorption maximum to longer wavelengths, whereas basic environments shift the absorption to shorter wavelengths (high frequency). They attributed these changes to intermolecular solventsolutes interaction forces that alter the energy differences between the ground and excited state of the absorbing species. This implies that pH has a significant effect on absorption of radiation by the dissolved species, and therefore, there is a need to optimise the best pH value for best results. In this study, the absorbing species showed max shift to lower wavelengths under strongly basic condition. In extremely strong acidic conditions, the proton from the acid influences electron generation process, by competing with adsorbed O2 which acts as electron scavengers, contributing to reduced photodegradation at low pH. This could be due to the decrease in the formation of the superoxide needed for oxidation of the organic matter. Our results also show that pH has an influence on the process of photocatalyst degrading the organic matter

Fig. 5 Effect of pH on photodegradation

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in water. Thus, the photodegradation was carried out at pH value 6.8 which showed best degradation results. Kinetics of photodegradation of starch The rate of degradation of starch was spectrophotometrically monitored, and the results obtained are presented in Fig. 6. Figure 6 shows the peaks to appear at 350 and 280 nm which can be attributed to the formation of starchiodine complex. This is similar to the degradation process of the leached DOC from maize tassels in Fig. 4 where the analyte in this solution decreased with increase in time. However, the peak observed at 590650 mm contributed by chlorophyll in the maize tassels is absent in Fig. 5 spectra. The data obtained from the starch degradation were plotted against time, and the results obtained were presented in Fig. 7. As observed in Fig. 7, the DOC decayed exponentially following a first-order kinetics. Thus, the degradation may be a unimolecular reaction and that other species present do not affect the photooxidation process of starch. Such a decay process may be expressed by a mass balance equation expressed in Eq. 6. aA bB C 6

The rate expression in Eq. 9 can be written as ln C = kt upon integration, Langergreg (1898) first-order kinetics. To confirm that the reaction was first order, a plot of ln C against time t should give a straight line. The symbol C refers to the concentration of the species of interest, k is the first-order rate constant and t is time (Rocha and Walker 1995). The experimental data obtained from the starch degradation experiment were treated with the Langergreg (1898) first-order kinetics, and a plot of ln C against time t obtained was presented in Fig. 8. The plot is a straight line with a linear R2 of 0.997 and a decay constant of 0.623 mg s1. The experimental data were also analysed using Ho et al. (2000) secondorder kinetics. This also served to investigate molecularity of the degradation mechanism and the ratecontrolling steps as well. The second-order kinetic models are expressed as is given by Eq. 10 dC k C 2 dt A 10

Upon integration, this gives Eq. 11 1 kt A C 11

From Eq. 6, the rate of disappearance of species A and B is given by Eq. 7 r k Aa Bb While the rate of appearance of C is given by Eq. 8 r k C : 8 7

Equation 8 is a first-order growth rate expressed by Eq. 9 (Dykaar and Kitanidis 1996; Wu and Nofziger 1999). dC k C dt A 9

1 A plot of C against time t was obtained as represented in Fig. 9. The plot was a straight line with a poor fit having a correlation coefficient R2 of 0.809. This linear regression coefficient is lower than that obtained in the the Lagergren first-order kinetics of 0.997, confirming that the degradation was therefore unimolecular and did not require any other substance except the photocatalyst and a source of light.

Fig. 6 Results of photooxidation of starch solution; degradation times in minutes of A =0, B =70 and C = 190

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Fig. 7 Concentration profiles of photodegradation of starch Fig. 9 Second-order kinetics plot for degradation of starch

Application of the photocatalyst To establish the stability of the photocatalyst immobilised on the sintered glass substrate, a series of experiments were carried out. This involved treating the photocatalyst material with strong mineral acids followed by exposing the immobilized photocatalyst to DOC for 12 h (reaction time).Tea leaves and seaweed were used as sources of DOC. The dissolution procedure for the biosorbents used by Mwangi et al. (2012) was adopted. A summary of the rate constant values for the degradation of DOC from various sources is presented in Table 1. Results obtained in Table 1 show that the photodegradation of DOC from materials studied in this work favoured firstorder kinetics. The rate constant values for the different materials were comparable. Materials such as tea leaves leached a golden colour into the solution, while seaweed material leached a thick green colour. In both cases, the rates of photodegradation were relatively lower. This could be attributed by the fact that plants contain a wide range of organic compounds such as sugars, starch, proteins, carbohydrates, lignins, waxes, resins and organic acids (Httenschwiler and Vitousek 2000). Naturally some of these compounds especially the simple ones such as proteins, organic acids, starches and sugars degrade rapidly, while the bulk and complex compounds such as proteins, fats, waxes and resins will require relatively longer periods to degrade as they break down slowly ( Kosobuchi

and Buszewki 2011). This implies that DOC from the plant origin has an increased number of oxidisable species in solution to interact with the superoxide-oxidising agent contributing to the observed phenomenon. This is simply due to the increased reducible organics in solution. However, the rate of DOC degradation in this study was monitored by determining the rate of starch degradation. It was also observed that the degradation rate for starch in the standard was slightly higher than that of maize tassels (see Tables 1 and 2). This observation could be explained by a high number of reducible organics in maize tassels as compared to the refined starch. A similar explanation could be given for the observation made on seaweeds. However, irrespective of the source of DOC, all the observed rate constants for the degradation of the active component, that is, starch analyte were in close agreement. This may be explained by the fact that the degradation process is first order and is not dependent on other species in solution (Dykaar and Kitanidis 1996; Wu and Nofziger 1999). Re-use of photocatalyst A series of experiments were done to study the effect of repeated use and exposure to strong acid environments. This was done to establish if the efficiency of photocatalyst to degrade DOC was affected by repeated use. The results obtained are presented in Table 2. The results in Table 2 show that based on the initial rate constants in Fig. 4, the efficiency of the reactor was not
Table 1 Rate constant values (K) for the degradation of DOC from various sources for both first- and second-order kinetics DOC source Starch Tea leaves Maize tassels Seaweed

Fig. 8 First-order kinetics plot for degradation of starch

First-order kinetics 0.623 K value/mgs1 2 R values 0.997 Second-order kinetics K values/mgs1 2.040 R2 values 0.856

0.594 0.945 1.772 0.667

0.622 0.986 0.642 0.853

0.581 0.957 0.658 0.834

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compromised by the exposure of the reactor to various hostile environments. This could be a result of the calcination process which is a thermal treatment process (Kim et al. 2002). Thermal treatment process in the presence of air may result in a good bonding between the glass material and the photocatalyst. In a related study, Paz and Heller (1997) reported the diffusion of sodium oxide from the soda lime glass into the titanium. They studied the abrasion resistance on photocatalytically self-cleaning windows and windshields with TiO2 films prepared by a solgel process. These observations may be explained by the fact that the degradation process is first order and therefore not dependent on other species in the media (Dykaar and Kitanidis 1996; Wu and Nofziger 1999). In order to establish the number of runs, the photoreactor can be used and retain its efficiency, a procedure that involved 100 runs for a period of a hundred days was used for the study, and the change in rate constant was monitored. It was established that the performance did not drop to below 95 % relative to the initial experiments. The results obtained in this study show that the efficiency of the reactor was not compromised by the length of exposure of the reactor to various hostile environments. Photodegradation of coloured solutions The photodegradation process of the chlorophyll colour in maize tassels was monitored at 618 nm. Scheme 1 shows the chemical structure of Chlorophyll-a. The photodegradation process gave a decay rate constant of 1.50 mgs1 and a regression coefficient (R2) of 0.9743. This may imply that when degrading DOC which contains coloured substances, the rate of degradation of the coloured substance would be higher relative to values from non-coloured species. The most likely explanation is that the coloured species injects electrons into the conduction band of the TiO2, increasing its photooxidation efficiency and therefore giving a relatively larger magnitude of photodegradation (Hilgendorff and Sundstro 1998). The process involves the excitation of dye molecules with visible light (Eq. 12) and the subsequent injection of electrons into the TiO2 photocatalyst (Eq. 13). hv dye ! dye* photocatalyst dye* ! dye e 12 13

Scheme 1 The chemical structure of Chlorophyll-a

The presence of double bonds in chlorophyll contributes to high extinction coefficients of this material in the visible region, enhancing photosensitization of the phtotocatalysts large band gap, thus accelerating its photocatalytic process (Zhoua et al. 2002). Compounds with double bonds also undergo bond cleavage followed by bond formation upon irradiation with particular light wavelengths (Zimmerman and Grunewald 1966). This may possibly also explain the reason why degradation of coloured solutions in this study had a higher rate than starch which has no double bonds as observed in the study.

Conclusions The photocatalytic activity of the Fe-doped TiO2 was activated using natural light. That is, the band gap of TiO2 was extended to the visible range. The band gap was narrowed by using ferric nitrate (as a source of Fe dopant) which is a transition metal, dopant, thus achieving the desired photoactivity. The XRD diffraction pattern showed that the crystallinity of metal-doped catalysts was changed after the doping process. Results of the degradation process demonstrated that the photocatalyst material could withstand different environments and still retain its efficiency. The degradation process was found to be most effective at the

Table 2 Rate constant values for repeated degradation of DOC from various sources DOC source Starch Tea Maize Seaweed leaves tassels 0.575 0.968 0.608 0.978 0.588 0.954

K value first-order kinetics/mgs1 0.622 R2 values first-order kinetics 0.976

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physiological pH of water (6.57.0) hence suitable for treatment of natural contaminated water containing DOCs at the point of use. The photocatalytic material was found to regenerate itself in the presence of visible light and therefore could be re-used in repeated applications (more than 100 times) without showing a significant loss of degradation efficiency. Mixtures of DOC and coloured solutions were degraded in various samples, implying that the degradation process was not dependent on intermediate or other species present in solution. This could be interpreted to mean that the photocatalyst may offer enhanced consumer appreciation because turbid or coloured water can effectively be treated with Fe(III)-doped TiO2 photocatalyst. Based on the results obtained, one can easily calculate the rate of photodegradation of DOC using the area of the coated surface, the mass of the degraded DOC and the time taken to degrade this mass. In our study, the photocatalyst was coated on a disc of area 12.57 cm2. Using this photoreactor, a total mass of 0.623 mg of DOC was degraded every second. These values translate to 1,000 mg (1 g) of the same material destroyed in 26.75 min using this type of reactor cell. We conclude that there is a great potential of application of this photoreactor to be used in tandem with biomass sorbents (which produce secondary pollution) applied in the purification of water for domestic consumption.
Acknowledgments IW Mwangi is grateful to OPCW (Organisation for Protection of Chemical Weapons) for running cost of this project and the University of Johannesburg (UJ) for registration and bursary, the Analytical/Environmental research group for helpful discussion and Kenyatta University for granting study leave.

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