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41 (2007) 379 386

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Hydroxyapatite-supported AgTiO2 as Escherichia coli disinfection photocatalyst$

M. Pratap Reddy, A. Venugopal, M. Subrahmanyam
Catalysis and Physical Chemistry Division, Indian Institute of Chemical Technology, Hyderabad 500 007, India

art i cle info

Article history: Received 26 October 2005 Received in revised form 6 September 2006 Accepted 20 September 2006 Available online 29 November 2006 Keywords: Hydroxyapatite (HAP) AgTiO2 AgTiO2/HAP composite catalyst Escherichia coli (E. coli) Photocatalytic bactericidal activity


A series of hydroxyapatite (HAP), 1 wt% AgTiO2 (AT1), 1 wt% Ag-HAP and 5 wt% AT1/HAP composite catalysts were prepared by incipient wetness and mechanical mixing methods. They were characterized by X-ray diffraction (XRD), FT-IR, SEM and ESCA analyses and their photocatalytic bactericidal activities were measured in suspension using Escherichia coli (E. coli), a water pollutant indicator. The surface analysis revealed that the Ag/Ti ratio is found to be ca. 0.0273 and also it indicated that the titania is present in the form of Ti4+ and Ag is present as metallic silver. Both the XRD and ESCA analyses conrmed the phase of metallic Ag particles, which played a signicant role on the bactericidal activity of the Ag doped TiO2 catalysts. The FT-IR analysis of HAP revealed that the peak intensity is due to the absorbance of surface PO3 group centered at wave number 1030 cm1 and is drastically 4 decreased upon exposure to UV for 1 h. The HAP displayed high amount of bacteria adsorption, ca. 80% during the dark experiments compared to other catalytic systems tested. The cumulative photocatalytic properties of AT1/HAP catalytic system resulted in 100% E. coli bacteria reduction within 2 min. & 2006 Elsevier Ltd. All rights reserved.



Application of photocatalysis as a remedy to the environmental problems has increased tremendously in the recent past (Blake et al., 1999; Ljubas, 2005; Dunlop et al., 2002). Presence of bacterial pathogens in drinking water is one of the perennial problems. Generally chlorine has been widely used for the disinfection of water, resulting in chloroorganic compounds during the treatment which are highly carcinogenic (Fujishima et al., 2000). Photocatalysis is a suitable method for disinfection of pathogenic bacteria present in drinking water. There are some reports concerning the photocatalytic removal of organic, inorganic and microbial pollutants (RincOn and Pulgarin, 2005) for the purication of water and wastewater treatment. The TiO2 catalyst has been found to be a widely used component in various photocata$

lytic applications. The bactericidal activity upon addition of Ag to TiO2 tremendously enhanced (Vamathevan et al., 2004; Zhang et al., 2005). Titania immobilization on different supports like glass matrix, optical bers, pumice stone and stainless-steel plate were studied extensively (Xu et al., 1999; Noorjahan et al., 2003; Subba Rao et al., 2004). In this investigation we have prepared hydroxyapatite (HAP), a novel material and characterized for its photocatalytic application. HAP is the major inorganic component in natural bones and can be synthesized by chemical precipitation, solid-state reaction, hydrothermal synthesis, solgel route and other routes (Brooks, 1981). It is used extensively as a matrix for the purication (Nonami et al., 2004) and fractionation of an array of biochemical substances, including enzymes, nucleic acids, hormones, and viruses (Brooks, 1981). The high bacterial adsorption of different bacteria onto HAP

Corresponding author. Tel.: +91 40 27193165; fax: +91 40 27160921.

IICT Communication no. 060305.

E-mail address: (M. Subrahmanyam). 0043-1354/$ - see front matter & 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.watres.2006.09.018


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material was described by Berry and Siragusa (1997). The Escherichia coli (E. coli) is a popular bacterial pollutant indicator in water and its presence makes water polluted with good number of pathogenic bacteria and its complete absence reckons no pathogenic bacteria and hence it is used as a treatment efciency substrate (Baker et al., 2000). To date, there is no report describing utilization of AgTiO2 supported over HAP. It can be used as an easy and efcient system for the complete removal of bacterial pathogens in drinking water.


Materials and chemicals

Titanium dioxide (P-25, 80% anatase and 20% rutile, of a specic area 50 m2/g) was from the Degussa Corporation. The active precursor salts, viz. calcium nitrate tetrahydrate, diammonium hydrogen phosphate, ammonium hydroxide, silver nitrate, ethanol and sodium chloride are from s.d. FineChem are of analytical grade quality. The E. coli broth (LuriaBertani) and E. coli agar (Luria-Bertani) are from SigmaAldrich and the E. coli bacteria used was supplied by the Microbial Type Culture Collection (MTCC), Institute of Microbial Technology (IMTECH), India and sterile distilled water was used in all the experimental studies.

slants and they were grown overnight at 37 1C by constant agitation (100 rpm) under aerobic conditions. The bacteria was subcultured from 50 to 500 ml ask having 250 ml broth and incubated aerobically (37 1C, 100 rpm) upto getting a maximum OD of 0.8 at 600 nm by UV-DRS. At exponential growth phase, bacterial cells were collected by centrifugation at 4000 rpm (10 min, 4 1C) and the bacterial pellet was washed three times with saline water (0.9% NaCl solution) in order to remove the culture media components. Finally the resulting pellet was resuspended in sterile saline water and diluted to cell density of 107 colony forming units (CFU)/ml by serial dilution method using sterile saline water. This culture solution was stored at 4 1C for 1 h and was used for further experiments in the entire study. The CFU counts/ml were performed with serial dilution and spread plate method using E. coli agar medium and the obtained counts were multiplied with a dilution factor.


Photocatalytic experiments


Preparation of catalysts

Ca10 (PO4)6 (OH)2 (HAP) denoted as HAP was prepared by the precipitation method (Venugopal and Scurrell, 2003). The TiO2 used was the commercial Degussa (P-25) and 1 wt% AgTiO2 (AT1) and 1 wt% AgHAP are made by impregnation technique. The 5 wt% TiO2/HAP and 5 wt% AT1/HAP catalysts were obtained by mechanical mixing method.


Characterization of catalysts

X-ray diffraction (XRD) patterns of fresh TiO2, HAP, 5 wt% TiO2/HAP, AT1, 1 wt% AgHAP and 5 wt% AT1 loaded on HAP support catalyst systems were obtained using Rigaku Miniex diffractometer with Ni ltered Cu-Ka radiation. The FT-IR spectra of all the fresh catalysts used were recorded on a Nicolet 740 FT-IR spectrometer using the KBr self-supported pellet technique in the frequency range of 4004000 cm1. Electron spectroscopy for chemical analysis (ESCA) was carried out with KRATOS AXIS 165 photoelectron spectroscopy using the Mg Ka (150 W) anode. The catalysts used for the chemical state and surface compositions were TiO2, AT1, HAP, 5 wt% TiO2/HAP and 5 wt% AT1/HAP. The Ag/Ti atomic ratios of the AT1 and 5 wt% AT1/HAP photocatalysts were determined by the intensities of Ti2p and Ag3d. The scanning electron microscopic (SEM) images were analyzed using model JEOL-JSM 5600 instrument.

The photocatalytic experimental setup was kept in laminar airow hood after proper sterilization. It consisted of a shaking unit with petriplates of capacity 50 ml, about 0.75 g/l catalyst and 25 ml of bacterial suspension were taken into each petriplate. The optimum catalyst concentration obtained with TiO2 for bactericidal activity in our recent study was about 0.75 g/l (Pratap Reddy and Subrahmanyam, 2006). The 250 W high-pressure mercury vapor lamp was provided as an illumination source from top, so that the radiation circumference covered all the plates under study. The lamp emitted radiation over a wavelength range of 320420 nm. The experimental setup was as shown in Fig. 1. An air-cooling fan was provided to reduce the temperature developed due to the irradiation. The bacterial suspension (N0 107 CFU/ml) with the catalyst was kept shaking at 50 rpm for proper agitation at room temperature. Experiments were conducted at room temperature and at pH of 6.5. One weight percent of Ag was doped onto TiO2 and HAP, as this was found to be the minimum concentration to observe a good amount of bacterial cell death. For the present investigation 5 wt% of TiO2 and 5 wt% AT1 supported on HAP catalysts were taken. A catalyst loading of 5 wt% was used since high bactericidal activity was observed over Hb zeolite support in our recent study (Pratap Reddy and Subrahmanyam, 2006). In view of this the 5 wt% loading of active component was selected for

Laminar Air Flow Hood

UV Light 250 W


Preparation of E. coli culture

Shaking Unit

Petri Plate with catalyst and E. coli suspension

E. coli was inoculated into fresh sterilized autoclaved E. coli broth of 10 ml in a 50 ml capacity conical ask from stock agar

Fig. 1 Illustration of experimental setup.


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testing its bactericidal efciency and a comparison with Hb zeolite support was made. All photocatalytic experiments were carried out for a period of 280 min under UV light irradiation. The various combinate catalyst systems tested for the present investigation were TiO2, HAP, 5 wt% TiO2/HAP, 1 wt% AgTiO2 (AT1), 1 wt% AgHAP and 5 wt% AT1 loaded on HAP support. Before performing photocatalytic experiments, the dark experiments were performed for $4 h over all the catalysts chosen for testing. This data gave the difference in bacterial adherence property on various catalyst systems under study, which is a key property that will inuence the bactericidal activity. Frequent samples of 0.1 ml were collected at 10 min interval time and inoculated into sterile 0.9 ml distilled water which was serially diluted and 0.1 ml of each dilution was inoculated into E. coli agar medium plates, the inoculum was spread and kept for colony growth at 37 1C for 48 h. The number of CFU/ml were noted after 48 h of time.

Anatase Ag

a b
Intensity (cps)

3.1. 3.1.1.

Results and discussion

Characterization of catalysts XRD analysis

d e f
0 20 40 Two theta (degree)
Fig. 2 XRD pattern of (a) TiO2, (b) HAP, (c) 5 wt% TiO2/HAP, (d) ATI, (e) 1 wt% AgHAP and (f) 5 wt% ATI/HAP.

XRD analysis revealed the reections due to Ca10 (PO4)6 (OH)2 phase in pure HAP, 1 wt% AgHAP, 5 wt% AT1/HAP, and 5 wt% TiO2/HAP catalysts and both the anatase (at 2y values of 25.31, 48.01, 53.91 and 55.01) and rutile phases (at 2y values of 27.41, 36.01, 54.21 and 56.51 (ICDD no.-86-1157)) were observed where TiO2 loadings were provided as shown in Fig. 2. The crystallinity of the prepared HAP was conrmed by the reections observed at 2y values of 31.71, 32.171, 33.01, 34.31, 46.61 and 49.51 (ICDD no.-86-0740). It is also found the metallic Ag phase at 2y of 32.21 and 46.21 (ICDD no.-87-0720) are found over Agdoped catalysts.




Scanning electron microscopy (SEM)


Infra red spectroscopy analysis

The comparative FT-IR spectrum analyzed for fresh HAP and after 1 h UV treatment in aqueous suspension is provided in Fig. 3. The spectra clearly represents the absorbance intensity at 1030 cm1 due to PO3 group and is drastically decreased 4 upon exposure to UV for 1 h and a similar observation is also reported by Nishikawa (2004).

SEM analysis photographs carried out for the samples of AT1, HAP, 1 wt% AgHAP and 5 wt% AT1/HAP are presented in Fig. 4. The SEM images of the catalysts illustrate the presence of particles of varying size and some pockets of agglomeration as seen from Fig. 4(a)1(d)1. The HAP, AgHAP and AT1/HAP sample photographs (Fig. 4(b)2(d)2) after 1 h dark adsorption period showed signicant bacteria adsorbed on the catalyst surface. Upon exposure to UV for a period of 1 h, there is a drastic reduction in the existence of bacteria over HAP, AgHAP and AT1/HAP catalysts.


ESCA 3.2. E. coli adsorption studies

ESCA analysis indicated the presence of metallic silver over the Ag-doped catalysts and the Ag/Ti ratio was found to be ca. 0.0273. This value contributes to the increase in photocatalytic activity as it stands in the range represented earlier, 0.01980.0595 (Sokmen et al., 2001). The comparative bactericidal activity performance of all the catalysts and the amount of Ag used are presented in Table 1. The relative intensities of O1s spectra (binding energy 532.1 eV) from the surface analysis comparison revealed that the O1 s contribution from hydroxyl radical is increased in the order of TiO2oAT1oHAPoAgHAPo5 wt% TiO2/HAPo5 wt% AT1/ HAP. This implies that more hydroxyl groups are present on the surface of 5wt% AT1/HAP for trapping the holes at TiO2, resulting in an enhanced photocatalytic activity (Milella et al., 2001).

E. coli adsorption studies were carried out in dark condition for AT1, HAP, 1 wt% AgHAP, 5 wt% TiO2/HAP and 5 wt% AT1/ HAP systems and they were monitored in terms of bacterial counts as CFU/ml as shown in Fig. 5(a). Furthermore, the pictorial inspection of SEM photographs for fresh catalysts as seen in Fig. 4(a)1(d)1 and the systems suspended in bacterial suspension in dark for 1 h as provided in Fig. 4(a)2(d)2 supplements the above relative differences in the adsorption amounts over various catalyst samples. From Fig. 5(a) it is observed that 80% and 20% of total bacterial count is adsorbed over bare HAP and Hb supports, respectively. In case of titania-supported HAP 55% of bacteria is adsorbed on to HAP surface within 80 min. It remains


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7.6 7 6 Absorbance 5 4 3 2 1 0 4000 3000 2000 1500 1000 500 400 After UV Before UV

Fig. 3 FTIR spectra of HAP before and after 1 h UV exposure.

Table 1 Characteristics of the catalysts used for the photocatalytic disinfection of water Catalyst XRD phase Timea (min) Ag/Tib Percent contribution from OH groups in O1s spectra of ESCA
11.4 40.1 46.0 19.8 71.0 78.0

TiO2 HAP 1 wt% 1 wt% 5 wt% 5 wt%

a b


Anatase and rutile Ca10 (PO4)6 (OH)2 Ag, Ca10 (PO4)6 (OH)2 Ag, TiO2 TiO2, Ca10 (PO4)6 (OH)2 Ag, TiO2, Ca10 (PO4)6 (OH)2

65 180 20 16 30 02

0.0274 0.0274 0.0273

Time taken for the complete removal of bacteria under UV irradiation (N0 107 CFU/ml). Ag/Ti atomic ratios from XPS analyses.

constant even after 280 min. No adsorption is observed on pure titania even after 280 min duration with a continuous stirring in dark whereas 10% bacterial adsorption is observed on titania-supported Hb. This observation is consistent with our recent report (Pratap Reddy and Subrahmanyam, 2006). In case of Ag-loaded catalysts of AT1, AgHAP, and AT1/HAP as seen in Fig. 5(b) 100% bacteria removal in suspension is observed within 90, 60 and 70 min, respectively. The observed bacterial adsorption trend is HAP4TiO2/ HAP4Hb 4TiO2/Hb and this may be due to the higher adsorption capacity of HAP than that of Hb. The adsorption of bacteria over HAP is due to nonspecic Van Der Walls and electrostatic attraction between positive calcium atoms of HAP and negatively charged surface of E. coli bacteria (Berry and Siragusa, 1997). In case of Ag-loaded catalysts the complete inactivation of bacteria from the solution may be due to two factors. It is the bactericidal activity attributed by the release of Ag+ ions into solution (Matsumura et al., 2003) and the other is due to adsorption property of HAP. However, in case of HAP, titania supported on Hb and on HAP catalysts, the inactivation of bacteria was due to adsorption and no bactericidal activity could be detected. The amount of Ag present in AgHAP is more than AT1/HAP due to which more reduction of bacteria was achieved in AgHAP. Between AgTiO2 and AgHAP, higher inactivation of bacteria is observed in

AgHAP, due to the Ag chemical activity and bacterial adherence property. The SEM photographs provided for bare (Fig. 4(a)1(d)1) and after 1 h dark soaking period in bacterial suspension over the catalyst systems AT1, HAP, Ag/HAP and AT1/HAP represents (Fig. 4(a)2(d)2) clearly that bare catalysts show titania and Agdoped titania dispersions on HAP crystals show Ag atoms dispersion on titania as well as HAP. Ag atoms are clearly observed on the catalyst surface of AgHAP and AT1/HAP (Fig. 4(c)2 and (d)2) and also these showed concentrated bacterial HAP surface during dark period. There is no bacteria adsorbed on AT1 and more or less equal adsorptions are observed on HAP, AgHAP and AT1/HAP catalysts after 1 h dark adsorption period.


Photocatalytic bactericidal activity performance study

From Fig. 6(a) it is observed that under UV irradiation titanialoaded HAP and Hb take 30 and 40 min duration for complete inactivation of bacteria whereas 180 and 65 min for HAP and titania, respectively. In order to improve the photocatalytic activity of titania-loaded HAP, Ag is doped to TiO2 and the same is supported on HAP. The results obtained in Fig. 6(b) show that the time taken for complete inactivation of bacteria is found to be only 16, 20 and 2 min for AT1, AgHAP and AT1/ HAP, respectively (see Table 1).


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Fig. 4 Scanning electron microscopy photographs of (a)13 AT1, (b)13 HAP, (c)13 1 wt% AgHAP and (d)13 5 wt% ATI/ HAP. Arrow (-) on the photographs pin point the E. coli bacteria.

The data in Fig. 6(a) seems to be due to the photocatalytic property exhibited by HAP under UV exposure where vacancies are formed on the surface of PO3 group of HAP. 4 This property is due to photoinduced electronic excitation and it is similar to the phenomena of the formation of electron trapped on oxygen vacancy in plasma-treated TiO2 (Nakamura et al., 2000). In the present case, the activation of

oxygen is due to the electron trapped on the vacancy of HAP that occurs and it is followed by the formation of Od 2 radical formation that is important for the photocatalytic oxidation of the bacteria adsorbed on HAP (Nishikawa, 2004; Pratap Reddy et al., 2006). The pictorial representation of HAP under UV illumination and the plausible mechanism for photocatalytic behavior is shown in Fig. 7(a). The same


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Bacterial survival (CFU/ml)

107 106 105 104 103 102 101 0 50 100 150 Time/min 200 250 300

a 107
Bacterial survival (CFU/ml)
106 105 104 103 102 101



150 200 Time/min



Bacterial survival (CFU/ml)

107 106 105 104 103 102 101

0 20 40 60 Time/min 80 100

b 107
Bacterial survival (CFU/ml)
106 105 104 103 102 101

0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 Time/min
Fig. 6 Inactivation of E. coli under UV illumination over catalyst systems. (A) () TiO2, (K) HAP, (m) 5 wt.% TiO2/Hb, (.) 5 wt.% TiO2/HAP and (B) () ATI, (K) 1 wt.% AgHAP, (m) 5 wt.% ATI/HAP. Photocatalyst 0.75 g/l.

Fig. 5 Adsorption of E. coli in dark condition over catalyst systems. (A) () TiO2, (K) hydroxyapatite (HAP), (m) 5 wt.% TiO2/Hb, (.) 5 wt.% TiO2/HAP and (B) () ATI, (K) l wt.% AgHAP, (m) 5 wt.% ATI/HAP. Photocatalyst 0.75 g/l.

does not exist with Hb zeolite support. Thus adsorption and photocatalytic property of HAP (called as sense and shoot approach) for the bactericidal effect is found to be high. Therefore it is clearly seen the bactericidal activity is enhanced in HAP and TiO2-supported HAP combination. The results in Fig. 6(b) indicate that photocatalytic activity of titania is enhanced by doping with Ag. This effect is due to the enhancement of OH radicals which are produced by the presence of Ag atom on TiO2 (Herrmann et al., 1988; Arabatzis et al., 2003). The pictorial representation of AT1/HAPsupported system and the plausible mechanism for bactericidal mode of activity is shown in Fig. 7(b). The actual mechanism of Ag present on titania under UV light is due to higher Fermi level position of titania over Ag. The electron transfer from TiO2 to the metallic Ag particles coated on TiO2 results in a space charge layer at the boundaries between Ag and TiO2. Thus Ag can help the electronhole separation by attracting the photoelectrons: TiO2 hn ! e p , Ag e 2e . Ag This enables the valency band photogenerated holes that are free to react with OH adsorbed on to the TiO2 to create hydroxyl radicals (dOH), which are able to degrade the

surrounding adsorbed bacteria: OH p ! OHd , OHd E:coli cultivable ! E:coli noncultivable. In the case of Ag, it can also improve the quantum yield by accelerating the removal and transfer of electrons from the catalyst particles to the molecular oxygen to form superoxide radicals. The superoxide radicals undergo further reactions to form hydroxyl radicals via the formation of hydrogen peroxide that is used for the oxidation of bacterial pollutants. (Vamathevan et al., 2004; Zhang et al., 2005). In case of AT1/ HAP there is an increase in the availability of bacteria for the photocatalytic activity of AT1 in view of the adsorption capacity of HAP and also due to the photocatalytic activity of HAP. The vacancies formed on the surface of excited PO3 4 group in UV illumination will lead to the formation of Od and 2 attack the surrounding bacteria adsorbed on HAP (Nishikawa, 2004; Nakamura et al., 2000; Teraoka et al., 2000). The cumulative bactericidal activity is more in the case of AT1/ HAP where complete 100% inactivation is achived within 2 min. But, in the case of AgHAP the bactericidal activity is not present in view of the absence of TiO2 and hence the overall performance of photocatalytic bactericidal is found to be less and the inactivation rate observed is within 20 min. Thus, AT1/HAP is found to be a highly efcient photocatalyst


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Photocatalytic behavior
O2 -

E. coli
O2 -

Ag eTiO2 h+ Hydroxyapatite OH eOH O2 -

UV Vacant Oxygen

O2 e3PO4


Fig. 7 The pictorial representation of UV-illuminated (a) HAP for photocatalytic behavior and (b) 5 wt% ATI supported HAP for bactericidal mode of activity.

and it can be easily prepared and it is a maintenance-free adsorbent that can be applied in the inactivation of E. coli bacteria from drinking water. The work is in progress to further develop the practical application of the present photocatalyst containing sense and shoot property during water treatment.



HAP was prepared by co-precipitation and 1 wt% Agtitania (AT1), 1 wt% AgHAP and 5 wt% AT1/HAP catalysts were prepared by wet impregnation method. The results of XRD and ESCA reveal that titania is present in the form of Ti4+ and silver as Ag0 in all the catalysts prepared. IR analysis of UVirradiated HAP conrmed the photocatalytic activity contribution is due to the changes of surface PO3 group. ESCA 4 analysis reported that the Ag/Ti ratio is 0.0273 in AT1 and 5 wt% AT1 loaded HAP showed improved photocatalytic activity. The SEM analysis of the fresh, dark and UV-exposed samples revealed that AgTiO2 supported on hydroxyapatite catalyst seems to be promising for the complete inactivation of E. coli. In SEM photographs a good amount of bacterial adsorption on HAP, AgHAP, AT1/HAP and no adsorption over AgTiO2 are observed. It is concluded that photocatalytic bactericidal activity is achieved in the combination system AT1/HAP due to (i) Ag effect (ii) synergistic effect of AgTiO2, and (iii) sense and shoot property of HAP.

One of the authors (MPR) acknowledge CSIR-New Delhi for SRF grant. The authors thank Dr. P.N. Sarma, Biochemical and Environmental Engineering Center (BEEC) for extending the laboratory facilities.

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