# Highly Active Rare-Earth-Metal La-Doped Photocatalysts: Fabrication, Characterization, and Their Photocatalytic Activity

Authors: S. Anandan; Y. Ikuma; V. Murugesan
Journal: International Journal of Photoenergy
 (2012)

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## Abstract

Efficient La-doped TiO2 photocatalysts were prepared by sol-gel method and extensively characterized by various sophisticated techniques. The photocatalytic activity of La-doped TiO2 was evaluated for the degradation of monocrotophos (MCPs) in aqueous solution. It showed higher rate of degradation than pure TiO2 for the light of wavelength of 254 nm and 365 nm. The rate constant of TiO2 increases with increasing La loading and exhibits maximum rate for 1% La loading. The photocatalytic activities of La-doped TiO2 are compared with La-doped ZnO; the reaction rate of the former is ~1.8 and 1.1 orders higher than the latter for the lights of wavelength 254 nm and 365 nm, respectively. The relative photonic efficiency of La-doped TiO2 is relatively higher than La-doped ZnO and commercial photocatalysts. Overall, La-doped TiO2 is the most active photocatalyst and shows high relative photonic efficiencies and high photocatalytic activity for the degradation of MCP. The enhanced photocatalytic activity of La-doped TiO2 is mainly due to the electron trapping by lanthanum metal ions, small particle size, large surface area, and high surface roughness of the photocatalysts.


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## Body

## 1. Introduction

The remarkable progress of scientific technologies in recent years has made extremely high demands on semiconductor material. Photocatalysis using semiconductors has been extensively performed worldwide to find solutions to energy and environmental problems, since the discovery of “Honda-Fujishima Effect” three decades ago. Among the semiconductors, outstanding stability and oxidative power make TiO2 the best semiconductor photocatalyst for environmental remediation and energy conversion processes [1–3]. However, the application of TiO2 is yet limited by the fast recombination of electron-hole pairs and their wide band gap, which corresponds with UV light [4]. Therefore, the studies of modifying TiO2 to reduce the electron-hole recombination and sensitization towards visible light have been extensively investigated. Metal ion doping has been widely performed on semiconductors to minimize electron/hole recombination and enhance their absorption towards visible light region [5–8]. For example, Choi et al. found that TiO2 doping with Fe3+, Mo5+, Ru3+, Os3+, Re5+, V4+, and Rh3+ increased photocatalytic activity in the liquid-phase photodegradation of CHCl3. However, (transition metal-) doped TiO2 suffers from a thermal instability or an increase in the carrier recombination centers [9]. Alternately, rare earth-doped metal oxides are potentially attractive materials for various optical and electronic applications because such materials exhibit unique physical and chemical properties such as fluorescence [10–12], persistent spectral hole burning [13–15], and ion conductivity [16]. Moreover, rare earth ions have radii larger than Ti4+, so they are mainly distributed on the surface when deposited onto TiO2, that keep large surface areas of TiO2 when treated at high temperatures. Atribak et al. [17] studied the catalytic oxidation of soot using La-modified TiO2 and concluded that TiO2 doped with 0.2% La exhibits best photocatalytic activity. In our previous studies, we developed La-doped ZnO photocatalysts and successfully applied for the degradation of organic pollutants in aqueous solution [18]. In the present study, we mainly focus on the synthesis of La-doped TiO2, since the photocatalytic activity of TiO2 was greater than ZnO. Moreover, the photocatalytic degradation of MCP using TiO2, ZnO, La-doped ZnO, and some of the commercial photocatalysts, carried out. Finally the photocatalytic efficiency of La-doped TiO2, compared with above-mentioned photocatalysts. Herein we report the synthesis, characterization, and application of La-doped TiO2 particles with series of lanthanum loading. La-doped TiO2 prepared by sol-gel method and extensively characterized using various sophisticated techniques. Photocatalytic activity of TiO2, La-doped TiO2, and other photocatalysts have evaluated by the degradation of MCP in aqueous solution. Photocatalytic decomposition of MCP is of great significance from the viewpoint of practical applications because MCP is one of the organophosphorous insecticides which are widely used in agriculture and animal husbandry. Also, MCP has been identified as endocrine disrupting chemicals (EDCs) which causes serious adverse effects on humans. The most serious among them are premature ageing, congenital abnormalities, and impotence [19]. It has been observed from the experimental results that La-doped TiO2 showed an excellent photocatalytic activity and relative photonic efficiency compared to other photocatalysts. Electron trapping by lanthanum metal ions, smaller particle size, large surface area, high porosity, and increase in surface roughness may be the reasons for the enhanced photocatalytic activity.


## 2. Experimental

### 2.1. Materials Preparation and Characterization

La-doped TiO2 was prepared by sol-gel method using titanium tetraisopropoxide (Analytical grade, Merck Ltd., India) and lanthanum nitrate hexahydrate (La (NO3)3·6 H2O) (Analytical grade, CDH, India) as titanium and lanthanum sources, respectively. The technical grade sample of monocrotophos (MCP) was received from Sree Ramcides Chemicals, India. HPLC grade acetonitrile was purchased from Merck, India. The lanthanum-doped TiO2 samples were prepared by sol-gel method. Required amount of Ti (O-Bu)4 was dissolved in absolute ethanol and the solution mixed vigorously in a solution containing appropriate amounts of water, acetic acid, and ethanol. Then lanthanum nitrate solution was added to the above sol to form a colloidal suspension. The resultant colloidal suspension was stirred and aged to form a gel. The gel was dried in vacuum and then ground. The resulting powder was calcined at 500°C and depending on the concentration of lanthanum nitrate; the photocatalysts were expressed in terms of weight percentage. The crystallinity of pure TiO2 and La-doped TiO2 photocatalysts was analyzed by X-ray powder diffraction (Model: PANalytical) with Cu-Kα radiation in the scanning range of 2θ between 10 to 80°. The accelerating voltage and applied current were 40 kV and 40 mA, respectively. Data were recorded at a scan rate of 0.02° s−1 in the 2θ range of 10° to 80°. The size of the crystallite was calculated from X-ray line broadening from the Scherrer equation:D=0.89λ/βcosθ,where D is the average crystal size in nm, λ is the Cu-Kα wavelength (0.15406 nm), β is the full width at half maximum, and θ is the diffraction angle. Specific surface area, pore volume, and pore diameter of the materials were determined from N2 adsorption-desorption isotherms at 77 K by using a Belsorb mini II sorption analyzer. Surface morphology of TiO2 and La-doped TiO2 photocatalysts were investigated by AFM (Digital Instruments, 3100) and FE-SEM-(Hitachi, S-4800). X-ray photoelectron spectroscopy (XPS—Thermo Electron Corporation Theta Probe) equipped with ultrahigh vacuum chambers were used to evaluate the presence of elements in La-doped TiO2 photocatalysts. Mg K-alpha X-rays (100 W) was used as the source at a takeoff angle of 5–75° and vacuum pressure of 10−6–10−7 Torr. The energy of monochromatic Mg K-alpha X-rays used for analysis is 1486.6 eV.


### 2.2. Photocatalytic Degradation Procedure and Analytical Methods

A cylindrical photochemical reactor setup was used as reported previously [20] for the degradation of MCP. The photocatalytic degradation was carried out by mixing 100 mL of aqueous MCP solution and 100 mg of photocatalyst. The experiments were performed at room temperature, and the pH of the reaction mixture was kept at solution pH. Before irradiation, the slurry was aerated for 30 min to reach adsorption equilibrium followed by UV irradiation at specific wavelength, 254 or 365 nm. Aliquots were withdrawn from the suspension at specific time intervals and centrifuged immediately at 1500 rpm. Then it was filtered through a 0.2 μm millipore filter paper to remove suspended particles. The filtrate was analyzed by HPLC and TOC to find out the extent of degradation and mineralization of MCP. The concentration of MCP was analyzed by HPLC instrument (Shimadzu, Model: SPD-10A VP) with a UV-Vis detector. In the HPLC analysis, Shim-pack CLC-C8 column (5 μm particle size, 250 mm length, and 4.6 mm inner diameter) and mobile phase of acetonitrile/water (6 : 4 v/v) were used with a flow rate of 1.0 mL min−1. An injection volume of 20 μL was used. The total organic carbon was determined by a TOC analyzer (Shimadzu, Model: 5000A) equipped with a single injection autosampler (ASI-5000). The concept of relative photonic efficiency (ξr) is very useful to compare catalyst efficiencies using a given photocatalyst (La-doped TiO2) material and a given standard photocatalyst (TiO2-Degussa P25) [21]. The relative photonic efficiency (ξr), was obtained by comparing the photonic efficiency of La-doped TiO2 with that of the standard photocatalyst (TiO2-Degussa P25). To evaluate ξr, a solution of MCP (40 mg L−1) with a pH of 5 was irradiated with 100 mg of TiO2 or La-doped TiO2 for 0.5 h. Then, relative photonic efficiency was calculated based on the above experiments.


## 2.1. Materials Preparation and Characterization

La-doped TiO2 was prepared by sol-gel method using titanium tetraisopropoxide (Analytical grade, Merck Ltd., India) and lanthanum nitrate hexahydrate (La (NO3)3·6 H2O) (Analytical grade, CDH, India) as titanium and lanthanum sources, respectively. The technical grade sample of monocrotophos (MCP) was received from Sree Ramcides Chemicals, India. HPLC grade acetonitrile was purchased from Merck, India. The lanthanum-doped TiO2 samples were prepared by sol-gel method. Required amount of Ti (O-Bu)4 was dissolved in absolute ethanol and the solution mixed vigorously in a solution containing appropriate amounts of water, acetic acid, and ethanol. Then lanthanum nitrate solution was added to the above sol to form a colloidal suspension. The resultant colloidal suspension was stirred and aged to form a gel. The gel was dried in vacuum and then ground. The resulting powder was calcined at 500°C and depending on the concentration of lanthanum nitrate; the photocatalysts were expressed in terms of weight percentage. The crystallinity of pure TiO2 and La-doped TiO2 photocatalysts was analyzed by X-ray powder diffraction (Model: PANalytical) with Cu-Kα radiation in the scanning range of 2θ between 10 to 80°. The accelerating voltage and applied current were 40 kV and 40 mA, respectively. Data were recorded at a scan rate of 0.02° s−1 in the 2θ range of 10° to 80°. The size of the crystallite was calculated from X-ray line broadening from the Scherrer equation:D=0.89λ/βcosθ,where D is the average crystal size in nm, λ is the Cu-Kα wavelength (0.15406 nm), β is the full width at half maximum, and θ is the diffraction angle. Specific surface area, pore volume, and pore diameter of the materials were determined from N2 adsorption-desorption isotherms at 77 K by using a Belsorb mini II sorption analyzer. Surface morphology of TiO2 and La-doped TiO2 photocatalysts were investigated by AFM (Digital Instruments, 3100) and FE-SEM-(Hitachi, S-4800). X-ray photoelectron spectroscopy (XPS—Thermo Electron Corporation Theta Probe) equipped with ultrahigh vacuum chambers were used to evaluate the presence of elements in La-doped TiO2 photocatalysts. Mg K-alpha X-rays (100 W) was used as the source at a takeoff angle of 5–75° and vacuum pressure of 10−6–10−7 Torr. The energy of monochromatic Mg K-alpha X-rays used for analysis is 1486.6 eV.


## 2.2. Photocatalytic Degradation Procedure and Analytical Methods

A cylindrical photochemical reactor setup was used as reported previously [20] for the degradation of MCP. The photocatalytic degradation was carried out by mixing 100 mL of aqueous MCP solution and 100 mg of photocatalyst. The experiments were performed at room temperature, and the pH of the reaction mixture was kept at solution pH. Before irradiation, the slurry was aerated for 30 min to reach adsorption equilibrium followed by UV irradiation at specific wavelength, 254 or 365 nm. Aliquots were withdrawn from the suspension at specific time intervals and centrifuged immediately at 1500 rpm. Then it was filtered through a 0.2 μm millipore filter paper to remove suspended particles. The filtrate was analyzed by HPLC and TOC to find out the extent of degradation and mineralization of MCP. The concentration of MCP was analyzed by HPLC instrument (Shimadzu, Model: SPD-10A VP) with a UV-Vis detector. In the HPLC analysis, Shim-pack CLC-C8 column (5 μm particle size, 250 mm length, and 4.6 mm inner diameter) and mobile phase of acetonitrile/water (6 : 4 v/v) were used with a flow rate of 1.0 mL min−1. An injection volume of 20 μL was used. The total organic carbon was determined by a TOC analyzer (Shimadzu, Model: 5000A) equipped with a single injection autosampler (ASI-5000). The concept of relative photonic efficiency (ξr) is very useful to compare catalyst efficiencies using a given photocatalyst (La-doped TiO2) material and a given standard photocatalyst (TiO2-Degussa P25) [21]. The relative photonic efficiency (ξr), was obtained by comparing the photonic efficiency of La-doped TiO2 with that of the standard photocatalyst (TiO2-Degussa P25). To evaluate ξr, a solution of MCP (40 mg L−1) with a pH of 5 was irradiated with 100 mg of TiO2 or La-doped TiO2 for 0.5 h. Then, relative photonic efficiency was calculated based on the above experiments.


## 3. Results and Discussion

### 3.1. Characterization of Photocatalysts

#### 3.1.1. XRD Patterns and TEM Analysis of TiO2 and La-Doped TiO2

XRD patterns of TiO2 and La-doped TiO2 are shown in Figure 1, in which the peaks marked “A” and “R” correspond with anatase and rutile phase, respectively. XRD analysis reveals that TiO2 and La-doped TiO2 photocatalysts was comprised of both anatase and rutile phases. The diffraction pattern of La-doped TiO2 photocatalysts was similar to that of pure TiO2. There are no peaks for the formation of composite metal oxides such as La2O3 in La-doped TiO2. It was observed that the peak at 2θ = 25.4° for La-doped TiO2 photocatalysts were slightly shifted to lower angles which shows that the presence of the large radius of La3+ (1.15 Å) may interstitially substitutes in TiO2 lattice rather substitute for relatively small radius Ti4+ (0.745 Å), and this cause, lattice distortion in La-doped TiO2 [22]. The crystal size was calculated using Scherer’s formula for the (101) plane of TiO2 and La-doped TiO2 photocatalysts, and the values are given in Table 1. The average grain size from the broadening of the (101) peak of anatase was 19–40 nm. The crystal size of La-doped TiO2 decreased with increase in La content, and their crystal size was less than that of pure TiO2. The decrease in crystal size was due to the incorporation of La-ion into TiO2, which decreases the grains growth [23]. The lattice parameters of La-doped TiO2 (Table 1) are a little smaller than the standard values of bulk TiO2 (a = 0.37728 nm, c = 0.95015 nm). The difference in lattice parameters shows that La3+ is successfully incorporated into the TiO2 lattice where it interstitially substitutes the Ti4+ ion sites as the ionic radius of La3+ (0.106 nm) is larger than that of Ti4+(0.061 nm) [24, 25]. The shift in the peak position and the change in the lattice parameters show that La3+ ions are replacing the Ti4+ ions. Representative TEM images of La-doped TiO2 are shown in Figure 2. Figure 2(a) reveals the uniform size of the TiO2 nanoparticles with a few aggregations, and the average particle diameter was estimated to be about 20 nm. HRTEM image (Figure 2(b)) revealed the presence of highly crystalline TiO2 nanoparticles in La-doped TiO2 photocatalysts. The electron diffraction pattern of La-doped TiO2 photocatalysts shown in Figure 2(c) further indicates that the samples were composed of highly crystalline TiO2 nanoparticles.Table 1
Physicochemical characteristic of TiO2 and La-doped TiO2 photocatalysts.
PhotocatalystCrystal size (D) nmLattice parameter (a) nmLattice parameter (c) nmUnit cellvolume (nm3)TiO240.100.377280.950150.13560.3 wt% La-TiO233.120.377720.950690.13570.5 wt% La-TiO230.560.377260.950510.13560.7 wt% La-TiO221.410.377220.950310.13571.0 wt% La-TiO219.870.377350.950240.13561.5 wt% La-TiO219.800.377540.950750.1356Pure ZnO53.110.32480.52050.04761.0% La-ZnO20.580.32670.51820.0472Figure 1
XRD patterns of TiO2 and La-doped TiO2: (a) TiO2, (b) 0.5 wt%, (c) 0.7 wt%, (d) 1.0 wt%, and (e) 1.5 wt% La-doped TiO2.Figure 2
TEM images of 1.0 wt% La-doped TiO2 (a) HR-TEM image (b) HR-TEM of the selective area, and (c) TEM image with electron diffraction pattern.


#### 3.1.2. Nitrogen Adsorption Measurements

The nitrogen adsorption-desorption isotherms of pure and La-doped TiO2 and their textural parameters are shown in Figure 3 and Table 2, respectively. TiO2 and La-doped TiO2 samples exhibit adsorption isotherms similar to Type II [26]. Type II isotherm is often observed when multilayer adsorption occurs on a nonporous solid. The surface area of pure TiO2 was about 118.5 m2/g while La-doped TiO2 exhibited a surface area of 98.36 m2/g. The decrease in the surface area for La-doped TiO2 can be attributed to the partial filling of the pores in TiO2 by La3+ nanoparticles. The pore diameters of pure and 1 wt% La-doped TiO2 were 2.718 nm and 4.267 nm, respectively. The decrease in surface area and corresponding increase in average pore diameter may be due to the collapse of considerably narrow pores to form broad pores in presence of La ions. Similar trend of results were previously observed for semiconductors doped with transition metals [27]. This shows that drastic modifications of pore structures take place when semiconductor oxides are doped with transition metals, and further, the effect probably depends on the individual metal characteristics. However, this trend is not common for all metal ion-doped semiconductors. The large pore of La-doped TiO2 also allows an easy diffusion of the pollutant molecules in and around the semiconductor, thus enhancing the adsorption of pollutant molecules and its intermediate on the surface of the photocatalysts. It is interesting to note that the surface area of TiO2 and 1 wt% of La-doped TiO2 are relatively higher than that of ZnO (53.11 m2/g) and 1 wt% of La-doped ZnO (39.56 m2/g) [18].Table 2
Textural properties of pure and La-doped semiconductors.
PhotocatalystABET/(m2g−1)Vp/(cm3 g−1)dp/(nm)TiO2118.50.10712.7181.0 wt% La-TiO298.360.1174.267Pure ZnO53.110.09421.1311.0% La-ZnO39.560.10532.378Figure 3
Nitrogen adsorption-desorption isotherms of TiO2 and 1 wt% La-doped TiO2.


#### 3.1.3. Atomic Force Microscope (AFM) and HR-SEM Analysis

The two-dimensional surface AFM images and surface roughness profiles of TiO2 and 1 wt% La-doped TiO2 are shown in Figures 4 and 5. From Figure 4(a), it could be observed that the size of TiO2 was not widely distributed and the grain size was big. The average roughness value (Rav) of pure TiO2 was 0.304 nm. However, for La-doped TiO2 the grains are sharpened and their size decreased to about 50%. The average roughness value (Rav) increased to 0.576 nm. So we safely conclude that the incorporation of La3+ into the lattice of TiO2 can control the grain growth and enhance the surface roughness of TiO2 photocatalysts. From the surface roughness values it can be revealed that La-doped TiO2 possesses high rough and porous surface than pure TiO2. These high rough and porous surfaces of La-doped TiO2 are beneficial to enhance the photocatalytic activity for the degradations of organic pollutants present in aqueous solution [28]. The high resolution-scanning electron micrographs (HR-SEM) of TiO2 and that of 1 wt% La-doped TiO2 are presented in Figures 6(a) and 6(b). TiO2 particles in Figure 6(a) seem to be well separated with regular shape. The morphology of TiO2 appears to be retained in 1 wt% La-doped TiO2 (Figure 6(b)) with random particle size distributions.(a) AFM image and (b) surface roughness profile of TiO2.
(a)(b)(a) AFM image and (b) surface roughness profile of 1.0 wt% La-doped TiO2.
(a)(b)HR-SEM pictures of (a) TiO2 and (b) 1.0 wt% La-doped TiO2.
(a)(b)


#### 3.1.4. X-Ray Photoelectron Spectroscopy (XPS) Analysis

Survey spectrum (Figure7(a)) of La-doped TiO2 photocatalyst exhibits the presence of Ti, O, and La elements. XPS spectrum of Ti-2p of TiO2 is shown in Figure 7(b). Ti 2p peak appeared as a single, well-defined, spin-split doublet with the typical interval of 6 eV between its two peaks which corresponds to Ti4+ in a tetragonal structure (i.e., Ti 2p1/2 and Ti 2p3/2, shown in Figure 7(b)). The binding energies of the peaks within the doublet were found to be 464.8 eV for Ti 2p1/2 and 459.0 eV for Ti 2p3/2 signal, and this was in good agreement with the binding energies of TiO2 found in the literature [29] (464.34 eV for Ti 2p1/2 peak and 458.8 eV for Ti 2p3/2 peak). The spectrum for Ti 2p of 1 wt% of La-doped TiO2 is also shown in Figure 7(b). It carries a similar feature as that of XPS spectrum, Ti 2p of TiO2. The XPS spectrum of O2− of TiO2 is shown in Figure 7(c). An intense signal about 531 eV due to O2− ions of TiO2 was observed. This peak was attributed to the Ti–O in TiO2 and OH groups on the surface of the photocatalysts [30, 31]. The shoulder about 532 eV of the main O 1s peak can be attributed to the presence of loosely bound oxygen of the surface-adsorbed CO32-, H2O, or O2 [32]. The XPS spectrum of O 1s of 1.0 wt% La-doped TiO2 is also shown in Figure 7(c). The spectrum of O1s broadened due to the incorporation of La3+ into the TiO2 lattice. The XPS spectrum of La 3d is shown in Figure 7(d). La3+ ions that incorporated into TiO2 lattice make interaction with oxidic sites of TiO2 (Ti–O–La) and appear to provide a broadened spectrum of La 3d. A Similar broad peak for La 3d spectrum of La3+ was also observed by Liqiang et al. [33] for La-doped TiO2 photocatalysts. These results conclude that La elements existed mainly as +3 valence in La-doped TiO2, Ti elements were both mainly as +4 valence, and both O elements had at least two kinds of chemical states, crystal lattice oxygen (1), and adsorbed oxygen (2). The presence of La, Ti, and O elements in TiO2 and La-doped TiO2 is also observed from the EDX spectra (See Figures  1sa and 1(b) in Supplementary material available on line at doi: 10.1155/2012/921412), and the results are consistent with XPS analysis.XPS spectra of pure and 1.0 wt% La-doped TiO2: (a) survey spectrum of TiO2 (b) Ti 2p (a = TiO2; b = 1.0 wt% La-TiO2) (c) O 1s (a = TiO2; b = 1.0 wt% La-TiO2), and (d) La 3d.
(a)(b)(c)(d)


### 3.2. Degradation Mechanism of La-Doped TiO2

To evaluate the photocatalytic activity of TiO2 and La-doped TiO2 a series of experiments were carried out for MCP degradation in aqueous suspension with the light of wavelengths 254 and 365 nm. The photocatalytic degradation of MCP follows a pseudo-first-order reaction. The apparent reaction rate constants (k) and t1/2 values of TiO2 and La-doped TiO2 are presented in Tables 3 and 4. For comparison the rate constant and t1/2 values of pure ZnO La-doped ZnO are also presented in Tables 3 and 4. La-doped TiO2 showed higher rate of degradation than TiO2 for the light of wavelength of 254 nm and 365 nm. The rate constant increased with increase in La loading up to 1.0 wt%, and with further increase in loading, the rate constant decreased. It was found that the reaction rate increased with the increase of lanthanum content (0.3–1 wt% La) at first and then declined when the cerium ion content (1.5 wt% La) exceeded its optimal value. In general, when increasing the metal ion concentration the carrier mobility decreased [34]. In the present study, the higher concentration of lanthanum in La-doped TiO2 photocatalysts decreased its crystallinity and carrier mobility, which led to reduction of the photocatalytic activity of TiO2. The reasons for the enhanced photocatalytic activity of TiO2 by the incorporation of lanthanum can be explained as follows. The incorporation of La3+ in the lattice of TiO2 decreases crystallite sizes and inhibits the electron-hole recombination on excitation of La-doped TiO2. Moreover it increased the surface roughness and provided more active surface area for photocatalytic reaction. The introduction of La3+ produces lattice swelling [35] and hence increases the surface roughness of La3+ (0.576 nm) than Ti4+ (0.304 nm). Thus, the increase in roughness of La3+ in La-doped TiO2 makes the structure loose and the grains activated which can be attributed to the high photocatalytic activity of TiO2. Further, an interesting observation was that the rate constant of 1 wt% La-doped TiO2 was higher than that of ZnO and 1 wt% La-doped ZnO [18] (Tables 3 and 4). Smaller particle size, high porosity, and high surface roughness are the reasons for the excellent photocatalytic activity of La-doped TiO2 than ZnO and La-doped ZnO. The half-life of degradation decreased with increase in La loading up to 1.0 wt%, and with further increase of La the half-life of degradation gets increase. The half-life of degradation with 1.0 wt% La-doped TiO2 was almost half the value of TiO2. These results also reveal the essential role of La3+ in La-doped TiO2 for the degradation of MCP.Table 3
Apparent reaction rate constants andt1/2 values for the degradation of MCP with 254 nm.
PhotocatalystApparent reaction rate constantk (× 10−2 min−1)t1/2 values (min)Correlation coefficient (R2 value)TiO26.011.550.9850.3 wt% La-TiO28.08.660.9760.5 wt% La-TiO29.57.290.9810.7 wt% La-TiO212.05.760.9901.0 wt% La-TiO214.04.950.9821.5 wt% La-TiO211.06.30.989Pure ZnO5.2513.200.9761.0% La-ZnO8.018.650.977MCP = 40 mg L−1, TiO2 or La-TiO2= 100 mg/100 mL, pH = 5, UV = 8 lamps, λ = 254 nm, adsorption equilibrium time = 30 min, and irradiation time = 60 min.Table 4
Apparent reaction rate constants andt1/2 values for the degradation of MCP with 365 nm.
PhotocatalystApparent reaction rate constantk (× 10−2min−1)t1/2 values (min)Correlation coefficient(R2 value)TiO25.313.080.9990.3 wt% La-TiO25.811.950.9950.5 wt% La-TiO26.710.340.9930.7 wt% La-TiO28.28.450.9941.0 wt% La-TiO29.07.70.9851.5 wt% La-TiO28.68.060.989Pure ZnO3.0013.200.9991.0% La-ZnO8.008.660.985MCP = 40 mg L−1, TiO2 or La-TiO2= 100 mg/100 mL, pH = 5, UV = 8 lamps, λ = 365 nm, adsorption equilibrium time = 30 min, and irradiation time = 60 min.


### 3.3. Photocatalytic Mineralization of MCP

Mineralization of hazardous pollutants by a cost-effective process is very important for industrial applications. To study the complete mineralization of MCP, the degradation was carried out with either TiO2 or La-doped TiO2 photocatalysts. The plot of total organic carbon value of MCP with time is illustrated in Figures 8 and 9 for the light of wavelength 254 nm and 365 nm, respectively. For comparison the mineralization results of pure ZnO and la-doped ZnO are also presented in Figures 8 and 9. It can be clearly seen from Figures 8 and 9 that the decrease of TOC concentration of MCP for La-doped TiO2 was relatively higher compared to pure TiO2. Decrease of TOC value of MCP showed maximum for 1 wt% La-doped TiO2 and achieved complete mineralization (100% TOC removal) of MCP within 3 h, whereas only 30% TOC removal was observed for pure TiO2 over the same period of irradiation time. Rapid mineralization of MCP over La-doped TiO2 can be associated with the suppression of electron-hole recombination by La3+ in the lattice of TiO2 and generation of more number of OH∙ radicals by oxidation of holes. OH∙ radicals are the primary oxidizing species which break down organic pollutants into a variety of intermediate products on the way to total mineralization to carbon dioxide and harmless inorganic ions [36]. The results demonstrated that 1.0 wt% La-doped TiO2 was found to be more active than other photocatalysts, namely, pure TiO2, 0.3 wt%, 0.5 wt%, 0.7 wt%, and 1.5 wt% La-doped TiO2 and those photocatalysts exhibited TOC removal of 30%, 28%, 75%, 70%, 75%, 87%, and 90%, respectively. 1.0 wt% La-doped TiO2 required shorter irradiation time for the complete mineralization of MCP compared to previously reported photocatalysts (pure ZnO, 1.0 wt% La-doped ZnO), and they disclosed only 28% and 70% TOC removal of MCP within 3 h, under the same experimental conditions [20]. Small particle size, high surface area, high surface roughness and porous surface of La-doped TiO2, and the suppression of electron-hole recombination by La3+ were the reasons for the high photocatalytic activity of La-doped TiO2 than other photocatalysts.Figure 8
Comparison of photocatalytic mineralization of MCP using TiO2 and La-doped TiO2 photocatalysts. (MCP concentration = 40 mg L−1; catalyst amount = 100 mg/100 mL; solution pH = 5; λ = 254 nm).Figure 9
Comparison of photocatalytic mineralization of MCP using TiO2 and La-doped TiO2 photocatalysts. (MCP concentration = 40 mg L−1; catalyst amount = 100 mg/100 mL; solution pH = 5; λ = 365 nm).


### 3.4. Relative Photonic Efficiency

The concept of relative photonic efficiency (ξr) affords comparison of catalyst efficiencies for the photocatalytic degradation of organic pollutants. To evaluate ξr, photocatalytic degradation of MCP was carried out over TiO2 (Degussa P-25) or La-doped TiO2 or other photocatalysts (ZnO and 1 wt% La-doped ZnO) with the lights of wavelengths 254 and 365 nm, and the results are presented in Table 5. The relative photonic efficiencies of La-doped TiO2 photocatalysts were greater than TiO2 and this revealed the effectiveness of metal-doped systems. The relative photonic efficiencies of light of wavelength 254 nm for La-doped TiO2 are greater than light of wavelength 365 nm. The results were in good agreement with degradation and mineralization studies. Comparing the high efficiency of La-doped TiO2 photocatalysts with standard catalyst (Degussa P-25), 1.0 wt% La-doped TiO2 is about 2.3 and 1.8 times more efficient than Degussa P-25 for the light of wavelength 254 nm and 365 nm, respectively. While comparing with La-doped ZnO photocatalysts, La-doped TiO2 was about 1.54 and 1.46 times higher for the light of wavelength 254 nm and 365 nm, respectively. The relative photonic efficiency of La-doped TiO2 photocatalysts was compared with already reported photocatalysts [21], and the values are shown in Table 5. 1 wt% La-doped TiO2 (254 nm) photocatalyst was about 6.13 times more efficient than Baker and Adamson whereas 9.32 times higher than Hombikat UV-100. Further, the relative photonic efficiency of 1 wt% La-doped TiO2 (254 nm) was relatively higher than the values reported for other commercial photocatalysts (Tioxide, Sargent-Weich and Fluka AG). It may be presumed that the incorporation of La3+ in the lattice of TiO2 greatly enhance the photocatalytic performance of TiO2 and hence showed high relative photonic efficiency value than all other photocatalysts.Table 5
Comparison of relative photonic efficiencies in the photocatalytic degradation of MCP by pure and La-doped semiconductors (TiO2 and ZnO).
PhotocatalystRelative photonic efficiency (ξr)TiO21.0 ± 0.01In this study1.0 wt% La-TiO2 (254 nm)2.33 ± 0.01In this study1.0 wt% La-TiO2 (365 nm)1.82 ± 0.01In this studyPure ZnO1.03 ± 0.01[18]1.0% La-ZnO (254 nm)1.51 ± 0.01[18]Baker and Adamson0.38 ± 0.02[18]Tioxide1.9 ± 0.1[21]Sargent-Welch2.1 ± 0.1[21]Fluka AG2.2 ± 0.2[21]Hombikat UV-1000.25 ± 0.02[21]MCP = 40 mg L−1, TiO2 or La-TiO2 = 100 mg/100 mL, pH = 5, UV = 8 lamps, λ = 254/365 nm, adsorption equilibrium time = 30 min, and irradiation time = 60 min.


### 3.5. Photocatalytic Reaction Mechanism

Metal ions doped on the semiconductors have been shown to improve the photocatalytic electron-transfer processes at the semiconductor interface [9, 37–39]. For example, the deposition of Au on TiO2 led to improvement in the efficiency of photocatalytic oxidation of thiocyanate ions [40]. Doped metal ions influence the photocatalytic activity of TiO2 by acting as electron (or hole) traps and by altering e-/h+ pair recombination rate through the following processes:Charge pair generation(1)TiO2+hν⟶ecb-+hνb+(2)Mn++hν⟶M(n-1)++hνb+(3)Mn++hν⟶M(n+1)++ecb-.Charge trapping(4)Mn++ecb-⟶M(n-1)+electrontrap(5)Mn++hνb+⟶M(n+1)+holetrap.Recombination(6)ecb-+hνb+⟶TiO2(7)M(n-1)++hνb+⟶Mn+(8)M(n+1)++ecb-⟶Mn+,
where Mn+ is a metal ion dopant. The energy level for Mn+/M(n-1)+ lies below the conduction band edge (Ecb) and the energy level for Mn+/M(n+1)+ above the valence band edge (Evb). In the present study, photocatalytic reaction mechanism for the degradation of MCP over La-doped semiconductor is speculated as follows. Under light illumination, La-doped TiO2 photocatalysts are exposed, and the electrons are excited from the valence band state to conduction band state. Liqiang et al. [33] demonstrated that surface oxygen vacancies and defects states by La doping could be favorable in capturing the photoinduced electrons during the process of photocatalytic reactions. Previously Chen et al. [41] reported that the introduction of new impurity states due to the incorporation of La3+ decreases the recombination of photogenerated electrons and holes. Hence, in the present study, we believe that the excited electrons in the conduction band transfer to the La3+ states, and the holes present in the valence band are available for the photocatalytic oxidation of MCP. The rare earth metal (here, La), which usually act as a reservoir for photogenerated electrons, promotes an efficient charge separation in La-doped TiO2 photocatalysts. In addition, small particle size, high surface area, high surface roughness, and porous surface of La-doped TiO2 were also the reason for the high photocatalytic activity of La-doped TiO2.


## 3.1. Characterization of Photocatalysts

### 3.1.1. XRD Patterns and TEM Analysis of TiO2 and La-Doped TiO2

XRD patterns of TiO2 and La-doped TiO2 are shown in Figure 1, in which the peaks marked “A” and “R” correspond with anatase and rutile phase, respectively. XRD analysis reveals that TiO2 and La-doped TiO2 photocatalysts was comprised of both anatase and rutile phases. The diffraction pattern of La-doped TiO2 photocatalysts was similar to that of pure TiO2. There are no peaks for the formation of composite metal oxides such as La2O3 in La-doped TiO2. It was observed that the peak at 2θ = 25.4° for La-doped TiO2 photocatalysts were slightly shifted to lower angles which shows that the presence of the large radius of La3+ (1.15 Å) may interstitially substitutes in TiO2 lattice rather substitute for relatively small radius Ti4+ (0.745 Å), and this cause, lattice distortion in La-doped TiO2 [22]. The crystal size was calculated using Scherer’s formula for the (101) plane of TiO2 and La-doped TiO2 photocatalysts, and the values are given in Table 1. The average grain size from the broadening of the (101) peak of anatase was 19–40 nm. The crystal size of La-doped TiO2 decreased with increase in La content, and their crystal size was less than that of pure TiO2. The decrease in crystal size was due to the incorporation of La-ion into TiO2, which decreases the grains growth [23]. The lattice parameters of La-doped TiO2 (Table 1) are a little smaller than the standard values of bulk TiO2 (a = 0.37728 nm, c = 0.95015 nm). The difference in lattice parameters shows that La3+ is successfully incorporated into the TiO2 lattice where it interstitially substitutes the Ti4+ ion sites as the ionic radius of La3+ (0.106 nm) is larger than that of Ti4+(0.061 nm) [24, 25]. The shift in the peak position and the change in the lattice parameters show that La3+ ions are replacing the Ti4+ ions. Representative TEM images of La-doped TiO2 are shown in Figure 2. Figure 2(a) reveals the uniform size of the TiO2 nanoparticles with a few aggregations, and the average particle diameter was estimated to be about 20 nm. HRTEM image (Figure 2(b)) revealed the presence of highly crystalline TiO2 nanoparticles in La-doped TiO2 photocatalysts. The electron diffraction pattern of La-doped TiO2 photocatalysts shown in Figure 2(c) further indicates that the samples were composed of highly crystalline TiO2 nanoparticles.Table 1
Physicochemical characteristic of TiO2 and La-doped TiO2 photocatalysts.
PhotocatalystCrystal size (D) nmLattice parameter (a) nmLattice parameter (c) nmUnit cellvolume (nm3)TiO240.100.377280.950150.13560.3 wt% La-TiO233.120.377720.950690.13570.5 wt% La-TiO230.560.377260.950510.13560.7 wt% La-TiO221.410.377220.950310.13571.0 wt% La-TiO219.870.377350.950240.13561.5 wt% La-TiO219.800.377540.950750.1356Pure ZnO53.110.32480.52050.04761.0% La-ZnO20.580.32670.51820.0472Figure 1
XRD patterns of TiO2 and La-doped TiO2: (a) TiO2, (b) 0.5 wt%, (c) 0.7 wt%, (d) 1.0 wt%, and (e) 1.5 wt% La-doped TiO2.Figure 2
TEM images of 1.0 wt% La-doped TiO2 (a) HR-TEM image (b) HR-TEM of the selective area, and (c) TEM image with electron diffraction pattern.


### 3.1.2. Nitrogen Adsorption Measurements

The nitrogen adsorption-desorption isotherms of pure and La-doped TiO2 and their textural parameters are shown in Figure 3 and Table 2, respectively. TiO2 and La-doped TiO2 samples exhibit adsorption isotherms similar to Type II [26]. Type II isotherm is often observed when multilayer adsorption occurs on a nonporous solid. The surface area of pure TiO2 was about 118.5 m2/g while La-doped TiO2 exhibited a surface area of 98.36 m2/g. The decrease in the surface area for La-doped TiO2 can be attributed to the partial filling of the pores in TiO2 by La3+ nanoparticles. The pore diameters of pure and 1 wt% La-doped TiO2 were 2.718 nm and 4.267 nm, respectively. The decrease in surface area and corresponding increase in average pore diameter may be due to the collapse of considerably narrow pores to form broad pores in presence of La ions. Similar trend of results were previously observed for semiconductors doped with transition metals [27]. This shows that drastic modifications of pore structures take place when semiconductor oxides are doped with transition metals, and further, the effect probably depends on the individual metal characteristics. However, this trend is not common for all metal ion-doped semiconductors. The large pore of La-doped TiO2 also allows an easy diffusion of the pollutant molecules in and around the semiconductor, thus enhancing the adsorption of pollutant molecules and its intermediate on the surface of the photocatalysts. It is interesting to note that the surface area of TiO2 and 1 wt% of La-doped TiO2 are relatively higher than that of ZnO (53.11 m2/g) and 1 wt% of La-doped ZnO (39.56 m2/g) [18].Table 2
Textural properties of pure and La-doped semiconductors.
PhotocatalystABET/(m2g−1)Vp/(cm3 g−1)dp/(nm)TiO2118.50.10712.7181.0 wt% La-TiO298.360.1174.267Pure ZnO53.110.09421.1311.0% La-ZnO39.560.10532.378Figure 3
Nitrogen adsorption-desorption isotherms of TiO2 and 1 wt% La-doped TiO2.


### 3.1.3. Atomic Force Microscope (AFM) and HR-SEM Analysis

The two-dimensional surface AFM images and surface roughness profiles of TiO2 and 1 wt% La-doped TiO2 are shown in Figures 4 and 5. From Figure 4(a), it could be observed that the size of TiO2 was not widely distributed and the grain size was big. The average roughness value (Rav) of pure TiO2 was 0.304 nm. However, for La-doped TiO2 the grains are sharpened and their size decreased to about 50%. The average roughness value (Rav) increased to 0.576 nm. So we safely conclude that the incorporation of La3+ into the lattice of TiO2 can control the grain growth and enhance the surface roughness of TiO2 photocatalysts. From the surface roughness values it can be revealed that La-doped TiO2 possesses high rough and porous surface than pure TiO2. These high rough and porous surfaces of La-doped TiO2 are beneficial to enhance the photocatalytic activity for the degradations of organic pollutants present in aqueous solution [28]. The high resolution-scanning electron micrographs (HR-SEM) of TiO2 and that of 1 wt% La-doped TiO2 are presented in Figures 6(a) and 6(b). TiO2 particles in Figure 6(a) seem to be well separated with regular shape. The morphology of TiO2 appears to be retained in 1 wt% La-doped TiO2 (Figure 6(b)) with random particle size distributions.(a) AFM image and (b) surface roughness profile of TiO2.
(a)(b)(a) AFM image and (b) surface roughness profile of 1.0 wt% La-doped TiO2.
(a)(b)HR-SEM pictures of (a) TiO2 and (b) 1.0 wt% La-doped TiO2.
(a)(b)


### 3.1.4. X-Ray Photoelectron Spectroscopy (XPS) Analysis

Survey spectrum (Figure7(a)) of La-doped TiO2 photocatalyst exhibits the presence of Ti, O, and La elements. XPS spectrum of Ti-2p of TiO2 is shown in Figure 7(b). Ti 2p peak appeared as a single, well-defined, spin-split doublet with the typical interval of 6 eV between its two peaks which corresponds to Ti4+ in a tetragonal structure (i.e., Ti 2p1/2 and Ti 2p3/2, shown in Figure 7(b)). The binding energies of the peaks within the doublet were found to be 464.8 eV for Ti 2p1/2 and 459.0 eV for Ti 2p3/2 signal, and this was in good agreement with the binding energies of TiO2 found in the literature [29] (464.34 eV for Ti 2p1/2 peak and 458.8 eV for Ti 2p3/2 peak). The spectrum for Ti 2p of 1 wt% of La-doped TiO2 is also shown in Figure 7(b). It carries a similar feature as that of XPS spectrum, Ti 2p of TiO2. The XPS spectrum of O2− of TiO2 is shown in Figure 7(c). An intense signal about 531 eV due to O2− ions of TiO2 was observed. This peak was attributed to the Ti–O in TiO2 and OH groups on the surface of the photocatalysts [30, 31]. The shoulder about 532 eV of the main O 1s peak can be attributed to the presence of loosely bound oxygen of the surface-adsorbed CO32-, H2O, or O2 [32]. The XPS spectrum of O 1s of 1.0 wt% La-doped TiO2 is also shown in Figure 7(c). The spectrum of O1s broadened due to the incorporation of La3+ into the TiO2 lattice. The XPS spectrum of La 3d is shown in Figure 7(d). La3+ ions that incorporated into TiO2 lattice make interaction with oxidic sites of TiO2 (Ti–O–La) and appear to provide a broadened spectrum of La 3d. A Similar broad peak for La 3d spectrum of La3+ was also observed by Liqiang et al. [33] for La-doped TiO2 photocatalysts. These results conclude that La elements existed mainly as +3 valence in La-doped TiO2, Ti elements were both mainly as +4 valence, and both O elements had at least two kinds of chemical states, crystal lattice oxygen (1), and adsorbed oxygen (2). The presence of La, Ti, and O elements in TiO2 and La-doped TiO2 is also observed from the EDX spectra (See Figures  1sa and 1(b) in Supplementary material available on line at doi: 10.1155/2012/921412), and the results are consistent with XPS analysis.XPS spectra of pure and 1.0 wt% La-doped TiO2: (a) survey spectrum of TiO2 (b) Ti 2p (a = TiO2; b = 1.0 wt% La-TiO2) (c) O 1s (a = TiO2; b = 1.0 wt% La-TiO2), and (d) La 3d.
(a)(b)(c)(d)


## 3.1.1. XRD Patterns and TEM Analysis of TiO2 and La-Doped TiO2

XRD patterns of TiO2 and La-doped TiO2 are shown in Figure 1, in which the peaks marked “A” and “R” correspond with anatase and rutile phase, respectively. XRD analysis reveals that TiO2 and La-doped TiO2 photocatalysts was comprised of both anatase and rutile phases. The diffraction pattern of La-doped TiO2 photocatalysts was similar to that of pure TiO2. There are no peaks for the formation of composite metal oxides such as La2O3 in La-doped TiO2. It was observed that the peak at 2θ = 25.4° for La-doped TiO2 photocatalysts were slightly shifted to lower angles which shows that the presence of the large radius of La3+ (1.15 Å) may interstitially substitutes in TiO2 lattice rather substitute for relatively small radius Ti4+ (0.745 Å), and this cause, lattice distortion in La-doped TiO2 [22]. The crystal size was calculated using Scherer’s formula for the (101) plane of TiO2 and La-doped TiO2 photocatalysts, and the values are given in Table 1. The average grain size from the broadening of the (101) peak of anatase was 19–40 nm. The crystal size of La-doped TiO2 decreased with increase in La content, and their crystal size was less than that of pure TiO2. The decrease in crystal size was due to the incorporation of La-ion into TiO2, which decreases the grains growth [23]. The lattice parameters of La-doped TiO2 (Table 1) are a little smaller than the standard values of bulk TiO2 (a = 0.37728 nm, c = 0.95015 nm). The difference in lattice parameters shows that La3+ is successfully incorporated into the TiO2 lattice where it interstitially substitutes the Ti4+ ion sites as the ionic radius of La3+ (0.106 nm) is larger than that of Ti4+(0.061 nm) [24, 25]. The shift in the peak position and the change in the lattice parameters show that La3+ ions are replacing the Ti4+ ions. Representative TEM images of La-doped TiO2 are shown in Figure 2. Figure 2(a) reveals the uniform size of the TiO2 nanoparticles with a few aggregations, and the average particle diameter was estimated to be about 20 nm. HRTEM image (Figure 2(b)) revealed the presence of highly crystalline TiO2 nanoparticles in La-doped TiO2 photocatalysts. The electron diffraction pattern of La-doped TiO2 photocatalysts shown in Figure 2(c) further indicates that the samples were composed of highly crystalline TiO2 nanoparticles.Table 1
Physicochemical characteristic of TiO2 and La-doped TiO2 photocatalysts.
PhotocatalystCrystal size (D) nmLattice parameter (a) nmLattice parameter (c) nmUnit cellvolume (nm3)TiO240.100.377280.950150.13560.3 wt% La-TiO233.120.377720.950690.13570.5 wt% La-TiO230.560.377260.950510.13560.7 wt% La-TiO221.410.377220.950310.13571.0 wt% La-TiO219.870.377350.950240.13561.5 wt% La-TiO219.800.377540.950750.1356Pure ZnO53.110.32480.52050.04761.0% La-ZnO20.580.32670.51820.0472Figure 1
XRD patterns of TiO2 and La-doped TiO2: (a) TiO2, (b) 0.5 wt%, (c) 0.7 wt%, (d) 1.0 wt%, and (e) 1.5 wt% La-doped TiO2.Figure 2
TEM images of 1.0 wt% La-doped TiO2 (a) HR-TEM image (b) HR-TEM of the selective area, and (c) TEM image with electron diffraction pattern.


## 3.1.2. Nitrogen Adsorption Measurements

The nitrogen adsorption-desorption isotherms of pure and La-doped TiO2 and their textural parameters are shown in Figure 3 and Table 2, respectively. TiO2 and La-doped TiO2 samples exhibit adsorption isotherms similar to Type II [26]. Type II isotherm is often observed when multilayer adsorption occurs on a nonporous solid. The surface area of pure TiO2 was about 118.5 m2/g while La-doped TiO2 exhibited a surface area of 98.36 m2/g. The decrease in the surface area for La-doped TiO2 can be attributed to the partial filling of the pores in TiO2 by La3+ nanoparticles. The pore diameters of pure and 1 wt% La-doped TiO2 were 2.718 nm and 4.267 nm, respectively. The decrease in surface area and corresponding increase in average pore diameter may be due to the collapse of considerably narrow pores to form broad pores in presence of La ions. Similar trend of results were previously observed for semiconductors doped with transition metals [27]. This shows that drastic modifications of pore structures take place when semiconductor oxides are doped with transition metals, and further, the effect probably depends on the individual metal characteristics. However, this trend is not common for all metal ion-doped semiconductors. The large pore of La-doped TiO2 also allows an easy diffusion of the pollutant molecules in and around the semiconductor, thus enhancing the adsorption of pollutant molecules and its intermediate on the surface of the photocatalysts. It is interesting to note that the surface area of TiO2 and 1 wt% of La-doped TiO2 are relatively higher than that of ZnO (53.11 m2/g) and 1 wt% of La-doped ZnO (39.56 m2/g) [18].Table 2
Textural properties of pure and La-doped semiconductors.
PhotocatalystABET/(m2g−1)Vp/(cm3 g−1)dp/(nm)TiO2118.50.10712.7181.0 wt% La-TiO298.360.1174.267Pure ZnO53.110.09421.1311.0% La-ZnO39.560.10532.378Figure 3
Nitrogen adsorption-desorption isotherms of TiO2 and 1 wt% La-doped TiO2.


## 3.1.3. Atomic Force Microscope (AFM) and HR-SEM Analysis

The two-dimensional surface AFM images and surface roughness profiles of TiO2 and 1 wt% La-doped TiO2 are shown in Figures 4 and 5. From Figure 4(a), it could be observed that the size of TiO2 was not widely distributed and the grain size was big. The average roughness value (Rav) of pure TiO2 was 0.304 nm. However, for La-doped TiO2 the grains are sharpened and their size decreased to about 50%. The average roughness value (Rav) increased to 0.576 nm. So we safely conclude that the incorporation of La3+ into the lattice of TiO2 can control the grain growth and enhance the surface roughness of TiO2 photocatalysts. From the surface roughness values it can be revealed that La-doped TiO2 possesses high rough and porous surface than pure TiO2. These high rough and porous surfaces of La-doped TiO2 are beneficial to enhance the photocatalytic activity for the degradations of organic pollutants present in aqueous solution [28]. The high resolution-scanning electron micrographs (HR-SEM) of TiO2 and that of 1 wt% La-doped TiO2 are presented in Figures 6(a) and 6(b). TiO2 particles in Figure 6(a) seem to be well separated with regular shape. The morphology of TiO2 appears to be retained in 1 wt% La-doped TiO2 (Figure 6(b)) with random particle size distributions.(a) AFM image and (b) surface roughness profile of TiO2.
(a)(b)(a) AFM image and (b) surface roughness profile of 1.0 wt% La-doped TiO2.
(a)(b)HR-SEM pictures of (a) TiO2 and (b) 1.0 wt% La-doped TiO2.
(a)(b)


## 3.1.4. X-Ray Photoelectron Spectroscopy (XPS) Analysis

Survey spectrum (Figure7(a)) of La-doped TiO2 photocatalyst exhibits the presence of Ti, O, and La elements. XPS spectrum of Ti-2p of TiO2 is shown in Figure 7(b). Ti 2p peak appeared as a single, well-defined, spin-split doublet with the typical interval of 6 eV between its two peaks which corresponds to Ti4+ in a tetragonal structure (i.e., Ti 2p1/2 and Ti 2p3/2, shown in Figure 7(b)). The binding energies of the peaks within the doublet were found to be 464.8 eV for Ti 2p1/2 and 459.0 eV for Ti 2p3/2 signal, and this was in good agreement with the binding energies of TiO2 found in the literature [29] (464.34 eV for Ti 2p1/2 peak and 458.8 eV for Ti 2p3/2 peak). The spectrum for Ti 2p of 1 wt% of La-doped TiO2 is also shown in Figure 7(b). It carries a similar feature as that of XPS spectrum, Ti 2p of TiO2. The XPS spectrum of O2− of TiO2 is shown in Figure 7(c). An intense signal about 531 eV due to O2− ions of TiO2 was observed. This peak was attributed to the Ti–O in TiO2 and OH groups on the surface of the photocatalysts [30, 31]. The shoulder about 532 eV of the main O 1s peak can be attributed to the presence of loosely bound oxygen of the surface-adsorbed CO32-, H2O, or O2 [32]. The XPS spectrum of O 1s of 1.0 wt% La-doped TiO2 is also shown in Figure 7(c). The spectrum of O1s broadened due to the incorporation of La3+ into the TiO2 lattice. The XPS spectrum of La 3d is shown in Figure 7(d). La3+ ions that incorporated into TiO2 lattice make interaction with oxidic sites of TiO2 (Ti–O–La) and appear to provide a broadened spectrum of La 3d. A Similar broad peak for La 3d spectrum of La3+ was also observed by Liqiang et al. [33] for La-doped TiO2 photocatalysts. These results conclude that La elements existed mainly as +3 valence in La-doped TiO2, Ti elements were both mainly as +4 valence, and both O elements had at least two kinds of chemical states, crystal lattice oxygen (1), and adsorbed oxygen (2). The presence of La, Ti, and O elements in TiO2 and La-doped TiO2 is also observed from the EDX spectra (See Figures  1sa and 1(b) in Supplementary material available on line at doi: 10.1155/2012/921412), and the results are consistent with XPS analysis.XPS spectra of pure and 1.0 wt% La-doped TiO2: (a) survey spectrum of TiO2 (b) Ti 2p (a = TiO2; b = 1.0 wt% La-TiO2) (c) O 1s (a = TiO2; b = 1.0 wt% La-TiO2), and (d) La 3d.
(a)(b)(c)(d)


## 3.2. Degradation Mechanism of La-Doped TiO2

To evaluate the photocatalytic activity of TiO2 and La-doped TiO2 a series of experiments were carried out for MCP degradation in aqueous suspension with the light of wavelengths 254 and 365 nm. The photocatalytic degradation of MCP follows a pseudo-first-order reaction. The apparent reaction rate constants (k) and t1/2 values of TiO2 and La-doped TiO2 are presented in Tables 3 and 4. For comparison the rate constant and t1/2 values of pure ZnO La-doped ZnO are also presented in Tables 3 and 4. La-doped TiO2 showed higher rate of degradation than TiO2 for the light of wavelength of 254 nm and 365 nm. The rate constant increased with increase in La loading up to 1.0 wt%, and with further increase in loading, the rate constant decreased. It was found that the reaction rate increased with the increase of lanthanum content (0.3–1 wt% La) at first and then declined when the cerium ion content (1.5 wt% La) exceeded its optimal value. In general, when increasing the metal ion concentration the carrier mobility decreased [34]. In the present study, the higher concentration of lanthanum in La-doped TiO2 photocatalysts decreased its crystallinity and carrier mobility, which led to reduction of the photocatalytic activity of TiO2. The reasons for the enhanced photocatalytic activity of TiO2 by the incorporation of lanthanum can be explained as follows. The incorporation of La3+ in the lattice of TiO2 decreases crystallite sizes and inhibits the electron-hole recombination on excitation of La-doped TiO2. Moreover it increased the surface roughness and provided more active surface area for photocatalytic reaction. The introduction of La3+ produces lattice swelling [35] and hence increases the surface roughness of La3+ (0.576 nm) than Ti4+ (0.304 nm). Thus, the increase in roughness of La3+ in La-doped TiO2 makes the structure loose and the grains activated which can be attributed to the high photocatalytic activity of TiO2. Further, an interesting observation was that the rate constant of 1 wt% La-doped TiO2 was higher than that of ZnO and 1 wt% La-doped ZnO [18] (Tables 3 and 4). Smaller particle size, high porosity, and high surface roughness are the reasons for the excellent photocatalytic activity of La-doped TiO2 than ZnO and La-doped ZnO. The half-life of degradation decreased with increase in La loading up to 1.0 wt%, and with further increase of La the half-life of degradation gets increase. The half-life of degradation with 1.0 wt% La-doped TiO2 was almost half the value of TiO2. These results also reveal the essential role of La3+ in La-doped TiO2 for the degradation of MCP.Table 3
Apparent reaction rate constants andt1/2 values for the degradation of MCP with 254 nm.
PhotocatalystApparent reaction rate constantk (× 10−2 min−1)t1/2 values (min)Correlation coefficient (R2 value)TiO26.011.550.9850.3 wt% La-TiO28.08.660.9760.5 wt% La-TiO29.57.290.9810.7 wt% La-TiO212.05.760.9901.0 wt% La-TiO214.04.950.9821.5 wt% La-TiO211.06.30.989Pure ZnO5.2513.200.9761.0% La-ZnO8.018.650.977MCP = 40 mg L−1, TiO2 or La-TiO2= 100 mg/100 mL, pH = 5, UV = 8 lamps, λ = 254 nm, adsorption equilibrium time = 30 min, and irradiation time = 60 min.Table 4
Apparent reaction rate constants andt1/2 values for the degradation of MCP with 365 nm.
PhotocatalystApparent reaction rate constantk (× 10−2min−1)t1/2 values (min)Correlation coefficient(R2 value)TiO25.313.080.9990.3 wt% La-TiO25.811.950.9950.5 wt% La-TiO26.710.340.9930.7 wt% La-TiO28.28.450.9941.0 wt% La-TiO29.07.70.9851.5 wt% La-TiO28.68.060.989Pure ZnO3.0013.200.9991.0% La-ZnO8.008.660.985MCP = 40 mg L−1, TiO2 or La-TiO2= 100 mg/100 mL, pH = 5, UV = 8 lamps, λ = 365 nm, adsorption equilibrium time = 30 min, and irradiation time = 60 min.


## 3.3. Photocatalytic Mineralization of MCP

Mineralization of hazardous pollutants by a cost-effective process is very important for industrial applications. To study the complete mineralization of MCP, the degradation was carried out with either TiO2 or La-doped TiO2 photocatalysts. The plot of total organic carbon value of MCP with time is illustrated in Figures 8 and 9 for the light of wavelength 254 nm and 365 nm, respectively. For comparison the mineralization results of pure ZnO and la-doped ZnO are also presented in Figures 8 and 9. It can be clearly seen from Figures 8 and 9 that the decrease of TOC concentration of MCP for La-doped TiO2 was relatively higher compared to pure TiO2. Decrease of TOC value of MCP showed maximum for 1 wt% La-doped TiO2 and achieved complete mineralization (100% TOC removal) of MCP within 3 h, whereas only 30% TOC removal was observed for pure TiO2 over the same period of irradiation time. Rapid mineralization of MCP over La-doped TiO2 can be associated with the suppression of electron-hole recombination by La3+ in the lattice of TiO2 and generation of more number of OH∙ radicals by oxidation of holes. OH∙ radicals are the primary oxidizing species which break down organic pollutants into a variety of intermediate products on the way to total mineralization to carbon dioxide and harmless inorganic ions [36]. The results demonstrated that 1.0 wt% La-doped TiO2 was found to be more active than other photocatalysts, namely, pure TiO2, 0.3 wt%, 0.5 wt%, 0.7 wt%, and 1.5 wt% La-doped TiO2 and those photocatalysts exhibited TOC removal of 30%, 28%, 75%, 70%, 75%, 87%, and 90%, respectively. 1.0 wt% La-doped TiO2 required shorter irradiation time for the complete mineralization of MCP compared to previously reported photocatalysts (pure ZnO, 1.0 wt% La-doped ZnO), and they disclosed only 28% and 70% TOC removal of MCP within 3 h, under the same experimental conditions [20]. Small particle size, high surface area, high surface roughness and porous surface of La-doped TiO2, and the suppression of electron-hole recombination by La3+ were the reasons for the high photocatalytic activity of La-doped TiO2 than other photocatalysts.Figure 8
Comparison of photocatalytic mineralization of MCP using TiO2 and La-doped TiO2 photocatalysts. (MCP concentration = 40 mg L−1; catalyst amount = 100 mg/100 mL; solution pH = 5; λ = 254 nm).Figure 9
Comparison of photocatalytic mineralization of MCP using TiO2 and La-doped TiO2 photocatalysts. (MCP concentration = 40 mg L−1; catalyst amount = 100 mg/100 mL; solution pH = 5; λ = 365 nm).


## 3.4. Relative Photonic Efficiency

The concept of relative photonic efficiency (ξr) affords comparison of catalyst efficiencies for the photocatalytic degradation of organic pollutants. To evaluate ξr, photocatalytic degradation of MCP was carried out over TiO2 (Degussa P-25) or La-doped TiO2 or other photocatalysts (ZnO and 1 wt% La-doped ZnO) with the lights of wavelengths 254 and 365 nm, and the results are presented in Table 5. The relative photonic efficiencies of La-doped TiO2 photocatalysts were greater than TiO2 and this revealed the effectiveness of metal-doped systems. The relative photonic efficiencies of light of wavelength 254 nm for La-doped TiO2 are greater than light of wavelength 365 nm. The results were in good agreement with degradation and mineralization studies. Comparing the high efficiency of La-doped TiO2 photocatalysts with standard catalyst (Degussa P-25), 1.0 wt% La-doped TiO2 is about 2.3 and 1.8 times more efficient than Degussa P-25 for the light of wavelength 254 nm and 365 nm, respectively. While comparing with La-doped ZnO photocatalysts, La-doped TiO2 was about 1.54 and 1.46 times higher for the light of wavelength 254 nm and 365 nm, respectively. The relative photonic efficiency of La-doped TiO2 photocatalysts was compared with already reported photocatalysts [21], and the values are shown in Table 5. 1 wt% La-doped TiO2 (254 nm) photocatalyst was about 6.13 times more efficient than Baker and Adamson whereas 9.32 times higher than Hombikat UV-100. Further, the relative photonic efficiency of 1 wt% La-doped TiO2 (254 nm) was relatively higher than the values reported for other commercial photocatalysts (Tioxide, Sargent-Weich and Fluka AG). It may be presumed that the incorporation of La3+ in the lattice of TiO2 greatly enhance the photocatalytic performance of TiO2 and hence showed high relative photonic efficiency value than all other photocatalysts.Table 5
Comparison of relative photonic efficiencies in the photocatalytic degradation of MCP by pure and La-doped semiconductors (TiO2 and ZnO).
PhotocatalystRelative photonic efficiency (ξr)TiO21.0 ± 0.01In this study1.0 wt% La-TiO2 (254 nm)2.33 ± 0.01In this study1.0 wt% La-TiO2 (365 nm)1.82 ± 0.01In this studyPure ZnO1.03 ± 0.01[18]1.0% La-ZnO (254 nm)1.51 ± 0.01[18]Baker and Adamson0.38 ± 0.02[18]Tioxide1.9 ± 0.1[21]Sargent-Welch2.1 ± 0.1[21]Fluka AG2.2 ± 0.2[21]Hombikat UV-1000.25 ± 0.02[21]MCP = 40 mg L−1, TiO2 or La-TiO2 = 100 mg/100 mL, pH = 5, UV = 8 lamps, λ = 254/365 nm, adsorption equilibrium time = 30 min, and irradiation time = 60 min.


## 3.5. Photocatalytic Reaction Mechanism

Metal ions doped on the semiconductors have been shown to improve the photocatalytic electron-transfer processes at the semiconductor interface [9, 37–39]. For example, the deposition of Au on TiO2 led to improvement in the efficiency of photocatalytic oxidation of thiocyanate ions [40]. Doped metal ions influence the photocatalytic activity of TiO2 by acting as electron (or hole) traps and by altering e-/h+ pair recombination rate through the following processes:Charge pair generation(1)TiO2+hν⟶ecb-+hνb+(2)Mn++hν⟶M(n-1)++hνb+(3)Mn++hν⟶M(n+1)++ecb-.Charge trapping(4)Mn++ecb-⟶M(n-1)+electrontrap(5)Mn++hνb+⟶M(n+1)+holetrap.Recombination(6)ecb-+hνb+⟶TiO2(7)M(n-1)++hνb+⟶Mn+(8)M(n+1)++ecb-⟶Mn+,
where Mn+ is a metal ion dopant. The energy level for Mn+/M(n-1)+ lies below the conduction band edge (Ecb) and the energy level for Mn+/M(n+1)+ above the valence band edge (Evb). In the present study, photocatalytic reaction mechanism for the degradation of MCP over La-doped semiconductor is speculated as follows. Under light illumination, La-doped TiO2 photocatalysts are exposed, and the electrons are excited from the valence band state to conduction band state. Liqiang et al. [33] demonstrated that surface oxygen vacancies and defects states by La doping could be favorable in capturing the photoinduced electrons during the process of photocatalytic reactions. Previously Chen et al. [41] reported that the introduction of new impurity states due to the incorporation of La3+ decreases the recombination of photogenerated electrons and holes. Hence, in the present study, we believe that the excited electrons in the conduction band transfer to the La3+ states, and the holes present in the valence band are available for the photocatalytic oxidation of MCP. The rare earth metal (here, La), which usually act as a reservoir for photogenerated electrons, promotes an efficient charge separation in La-doped TiO2 photocatalysts. In addition, small particle size, high surface area, high surface roughness, and porous surface of La-doped TiO2 were also the reason for the high photocatalytic activity of La-doped TiO2.


## 4. Conclusion

Highly efficient photocatalyst, La-doped TiO2, was successfully synthesized and characterized by various sophisticated techniques. XRD and TEM analysis revealed the presence of highly crystalline TiO2 nanoparticles. AFM results demonstrated that La-doped photocatalysts have rough and highly porous surface, which is a critical parameter to enhance the photocatalytic activity. The photocatalytic activity of La-doped TiO2 in the degradation of MCP was studied, and the results were compared with degradation results of La-doped ZnO photocatalysts. La-doped TiO2 photocatalysts were found to be very active, and its rate constant was 1.75 and 1.125 times higher than La-doped ZnO photocatalysts for the light of wavelength 254 nm and 365 nm, respectively. The relative photonic efficiency of La-doped TiO2 catalyst was relatively higher than that of previously reported and some of the commercial photocatalysts. Small particle size, high surface area, high surface roughness, and the suppression of electron-hole recombination by La3+ were the reasons for the high photocatalytic activity of La-doped TiO2 for the removal of MCP than other photocatalysts. It is concluded that incorporation of rare earth metal into the semiconductors has been proven to be a promising approach to improve the photocatalytic activity of semiconductors.



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*Source: 921412-2011-12-22.xml*