Characterization of La/Fe/TiO2 and Its Photocatalytic Performance in Ammonia Nitrogen Wastewater

La/Fe/TiO2 composite photocatalysts were synthesized by Sol-Gel method and well characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen-physical adsorption, and UV-Vis diffuse reflectance spectra (UV-Vis DRS). It is interesting that the doped catalysts were in anatase phase while the pure TiO2 was in rutile phase. In addition, the composites possessed better physical chemical properties in photocatalytic activity than pure TiO2: stronger visible-light-response ability, larger specific surface area, and more regular shape in morphology. The photodegradation results of ammonia nitrogen indicate that: the La/Fe/TiO2 had higher catalytic activity to ammonia nitrogen waste water compared pure TiO2 and the other single metal-doped TiO2. pH 10 and 2 mmol/L H2O2 were all beneficial to the removal of ammonia nitrogen by La/Fe/TiO2. However, the common inorganic ions of Cl−, NO3−, SO42−, HCO3−/CO32−, Na+, K+, Ca2+ and Mg2+ in water all inhibited the degradation of ammonia nitrogen. By balance calculation, at least 20% of ammonia nitrogen was converted to N2 during the 64.6% removal efficiency of ammonia nitrogen.

chemical properties of La-Fe-codoped TiO2 prepared by Sol-Gel method and characterized by XRD, SEM, EDS, and UV-Vis DRS; secondly, to study the photocatalytic activity of prepared doped TiO2 to ammonia nitrogen; thirdly, to discuss the effect of reaction solution pH, H2O2, and common inorganic ions on the degradation of ammonia nitrogen; finally, to disclose the conversion products of ammonia nitrogen during the photodegradation process.

Modification Methods
The photocatalysts were prepared by Sol-Gel method. The mixture solution of 8.5 mL tetrabutyl titanate dissolved in 20 mL anhydrous ethanol with stirring for 30 min was noted as solution A. Another solution containing 20 mL ethanol, 1.5 mL deionized water, and metal salts (La(NO3)3 and/or Fe(NO3) 3) in the required stoichiometry was noted as solution B. Solution B was pumped into solution A by half drop (ca. 0.05 mL) per second at ca. 30 °C. The mixture was hydrolyzed at room temperature for a period of time under vigorous stirring and finally the translucent sol was formed. The gel was prepared by aging the sol for two days at room temperature. The dry gel was gained after drying at 80 °C for 2 h. Finally, the gel was calcined at 500 °C at the heating rate of 2.5 °C/min in the muffle furnace for 2 h and was ground into powders for use.

Characterization
Powder X-ray diffraction (XRD) data were recorded on a D/Max-3c X-ray diffraction meter at 40 kV and 40 mA for monochromatized Cu Kα (λ = 1.5418 Å) radiation. Scanning electron microscopy (SEM) measurements were carried out on S-4800 type of field emission scanning electron microscope with energy dispersive spectrometer (EDS). The BET surface areas of the samples were obtained from the automatic analyzer (JW-004A, Beijing JWGB Sci.&Tech. Co.,Ltd, Beijing, China). UV-Vis diffuse reflectance spectra were achieved using a UV-Vis spectrophotometer (UV-2550, Shimadzu China Co., Ltd., Japan), and the absorption spectra were referenced to BaSO4.

Photocatalytic Removal Experiments and Analytical Methods
The photocatalytic degradation experiments were carried out in a XPA-7 photochemical reactor (Xujiang Electrical Mechanical Plant, Nanjing, China). The irradiation was provided by a 500 W Mercury lamp (Institute of Electric Light Source, Beijing, China), which mainly radiated 365 nm wavelenght of light and was positioned in the cylindrical quartz cold trap. The system was cooled by circulating water and maintained at room temperature. Before the irradiation, the suspension was magnetically stirred for 30 min in the dark to ensure adsorption equilibrium of ammonia nitrogen on the catalysts. For all the reactions, the irradiation lasted for 300 min. Approximately 5 mL of reaction solution was taken at given time intervals and centrifuged. The supernatant was analyzed by Nessler's reagent spectrophotometry [27] and the removal efficiency (R) was calculated by Formula (1) as follows: where C0 is the initial concentration of ammonia nitrogen and C is the concentration at reaction time t (min). In order to study the conversion of ammonia nitrogen, NO2-N and NO3-N were also detected by spectrophotometry methods [28,29]. In addition, the effects of H2O2 and common ions (Cl − , HCO3 − /CO3 2− , NO3 − , SO4 2− , Na + , K + , Ca 2+ , Mg 2+ ) in natural waters on ammonia nitrogen removal were investigated. Besides, all the experiments were performed at least twice and the mean values were reported.

XRD
The XRD patterns of P25, pure TiO2, La/TiO2 and La/Fe/TiO2 composites are shown in Figure 1. . This showed that the pure TiO2 prepared existed in the rutile phase while the doped catalysts in the anatase phase whether La/TiO2 or La/Fe/TiO2. It is interesting to find that the doped rare earth Lanthanum changed the crystal structure of TiO2 from rutile to anatase. Compared to P25, the crystallinity of doped TiO2 decreased as shown in Figure 1. Besides, there are no peaks for the formation of composite metal oxides such as La2O3 or Fe2O3 in doped TiO2, which might be ascribed to the fact that the concentration of La-doping and/or Fe-doping was so low and the overlapping of diffraction peaks due to TiO2, La2O3, and/or Fe2O3.

UV-Vis DRS
The UV-Vis DRS spectra of P25, TiO2, La/TiO2, Fe/TiO2, and La/Fe/TiO2 are depicted in Figure 2A. All the doped powders showed a redshift compared to P25 while undoped TiO2 exhibits an absorption edge to the visible light region due to the rutile phase. Besides, there is an obvious change of light absorption of La/Fe/TiO2 from ultraviolet to visible light due to the La-Fe-codoping. The redshift phenomenon indicates that the modified TiO2 broaden the scope of light response as anatase phase. In other words, the visible-light-response catalysts overcome the disadvantage of the broadband gap to a certain extent [30]. In addition, the absorption data were analyzed using the following well-known formula for near-edge optical absorption of semiconductors [31].
where α is the absorption coefficient, (hυ) is the photon energy, A is a constant, Eg is the optical gap, and the value of n is 1/2 for TiO2 [32]. To estimate the optical band gap, the plot of (αhυ) 2 versus (hυ) is shown in Figure 2B.  (B) Plots of (αhυ) 2 versus (hυ) for catalysts).

Surface Morphology Analysis
As seen from Figure 3, pure TiO2 ( Figure 3A) exhibits irregular shape and is agglomerated badly. However, after La and Fe co-doped, the reunion phenomenon is abated and is a relatively flat surface. Compared to Figure 3A and 3B, the more serious reunion phenomenon of pure TiO2 might be based on the large amounts of hydroxyl groups on the surface of pure TiO2 which would result in the strong hydrogen bonding between particles [33]. Further data for the composition of La/Fe/TiO2 photocatalysts were obtained by EDS: La accounted for 3.62% while Fe accounted for 0.62%. The result is consistent with the UV-Vis DRS and proves that elements lanthanum and iron were all loaded on the surface of TiO2.

Specific Surface Area Analysis
The specific surface area of P25, TiO2, La/TiO2, and La/Fe/TiO2 is 48.12, 65.57, 78.36, and 120.74 m 2 /g respectively. A significant increase in specific surface area of the doped samples was observed. The increase in specific surface area after doping may be caused by the decrease in the crystallite size of TiO2, as described in the XRD and SEM part, which is in agreement with Anandan's report that doping of rare earth could increase the surface area of TiO2 [34].

Degradation Performance of Ammonia Nitrogen Wastewater
A series of control experiments were designed to investigate the photocatlytic activity of prepared doped composites, and all the experiments were carried out with the same conditions of pH (ca. 10), catalyst amount (1 g/L), and 500 W mercury lamp. Figure 4 shows the result. After 5 h, about 15% of ammonia nitrogen was removed by direct photolysis or escaping from the reaction solution by magnetic stirring, while above 50% was removed by photocalytic degradation with catalyst. Furthermore, the doped catalysts showed higher photocatalytic activity on ammonia nitrogen removal than pure TiO2 by the analysis of first-order reaction kinetics as shown in Table 1. The best removal efficiency of ammonia nitrogen reached 64.6% with La/Fe/TiO2.  Anandan [34] reported that small particle size, high surface area, high surface roughness, and porous surface of La-doped TiO2 and the suppression of electron-hole recombination by La 3+ were the reasons for the high photocatalytic activity of La-doped TiO2, the characterization result of this study is consistent with their conclusion. Besides, Fe 3+ is born of the electron capture trap [23]. Under the synergy of La 3+ and Fe 3+ , the electron-hole pairs produced from catalyst under irradiation could be effectively separated and the catalytic activity of La/Fe/TiO2 was improved.

Effect of Different pH
The initial pH of the reaction solution might influence the surface charge of La/Fe/TiO2 and the existing form of ammonia nitrogen in water and finally affect the ammonia nitrogen removal efficiency. Firstly, the number of OH − increases with the pH increases gradually, and more ·OH would be generated induced by La/Fe/TiO2, resulting in promoting the removal rate of ammonia nitrogen. Secondly, there are two forms of ammonia nitrogen in water: NH3·H2O and NH 4+ . Proportion of NH3·H2O molecules increases as the pH increases in the solution. Thirdly, the space steric hindrance of NH3 is smaller than that of NH4 + , which is more conducive to the reaction of NH3 with ·OH. At last, the pHPZC (point of zero charge) of La/Fe/TiO2 is about 6.4 by analysis of Zeta potential. So, it is difficult for the attraction of ammonia molecules onto the surface of the catalyst in an acidic condition. All the analysis above demonstrates that ammonia nitrogen was removed rapidly in alkaline environment [35]. However, as shown in Figure 5, it did not favor the catalytic reaction at pH 10.9, which might be due to that excessive OH − in the solution. The following experiments would be performed at pH ca. 10.

Effect of H2O2
H2O2 is usually applied as a stimulator in TiO2 photocatalysis system to enhance the rate of photocatalytic oxidation [36,37]. In order to investigate the effect of H2O2 addition on ammonia nitrogen degradation by La/Fe/TiO2, experiments were conducted by varying the initial H2O2 concentration in the range of 0.01 to 10 mmol/L (0.01, 0.1, 0.5, 2, 10 mmol/L). As shown in Figure 6, addition of H2O2 promoted the removal rate of ammonia nitrogen. The removal rate reached 78.3% with H2O2 of 2 mmol/L. It is well known that H2O2 has strong absorbance in the range of 200-350 nm and could produce ·OH under UV irradiation (Formula (2)). Besides, as a kind of strong oxidizer, H2O2 can effectively capture the photoproduction electrons of TiO2 conduction belt and be converted to ·OH as Formula (3). So, the degradation was accelerated with the addition of H2O2.
However, excessive H2O2 would exhaust the generated OH ⋅ in the reaction solution (Formulas (4) and (5)) [38] to reduce the promotion. 2 Figure 6. The effect of H2O2 on the degradation of NH4 + -N with La/Fe/TiO2.

Effects of Inorganic Ions
There are eight common inorganic ions in natural water [39], including Na + , K + , Ca 2+ , Mg 2+ , Cl − , SO4 2− , NO3 − , and HCO3 − /CO3 2− , and the concentrations are all 0.1 mmol/L. They might affect the removal of pollutants in water. Results of the effects of cations and anions on ammonia nitrogen degradation are shown in Figure 7.  As seen from Figure 7, at the same experimental conditions, all kinds of inorganic ions showed an obvious inhibitory effect on ammonia nitrogen removal. Sörensen indicated that NO3 − acted as an "inner filter" and reduces the UV light intensity in the photoreactor [40]. Thereby, addition of NO3 − decreased the degradation rate of pollutant in the reaction system. Besides, the inhibited effect increased as the reaction went on. The reason might be that excessive NO3 − was produced from the conversion of ammonia nitrogen (the content will be discussed below). It was reported that HCO3 − /CO3 2− is an effective ·OH scavenger [40]. It can react with ·OH to produce carbonate radicals, which are weak oxidizing reagents that hardly react with other pollutant molecules. Therefore, HCO3 − /CO3 2− displayed distinct inhibition effect on the degradation of ammonia nitrogen by La/Fe/TiO2. Cl − and SO4 2− also could react with ·OH like HCO3 − /CO3 2− , but the reaction ability was lower than NO3 − , and the inhibited effect was smaller than HCO3 − /CO3 2− . Since SO4 2− is double charged, it may display higher inhibition ability than Cl − . Na + , K + , Ca 2+ , and Mg 2+ are all in the highest and stable oxidation state and cannot capture electrons or holes in solution. It is hypothesized that these metal ions would not show significant impacts on the photo degradation of ammonia nitrogen by La/Fe/TiO2. As shown in Figure 7B, the four metal ions displayed inhibition effects on ammonia nitrogen removal, which could be attributed to the effect of Cl − ions co-present in the solution. The metal ions were used in their chloride salts. As described above, Cl − ions might inhibit the photo degradation due to the reaction with ·OH. Since K + and Na + are in the same elemental main group, they have similar properties. KCl showed similar effect as NaCl. In addition, Ca 2+ and Mg 2+ also have similar properties and they (CaCl2 and MgCl2) displayed similar trends. Furthermore, Ca 2+ and Mg 2+ displayed higher inhibition effects than NaCl and KCl at the same mole concentrations. This is expected since the concentration of Cl − in CaCl2 and MgCl2 solutions was twice of that in NaCl and KCl solutions [41]. Besides, Mg 2+ and Ca 2+ tend to form precipitation and adhere to the surface of the catalyst to reduce the photocatalytic efficiency in weak alkaline conditions [42].

Analysis of Degradation Products of Ammonia Nitrogen
WuJie [43] mentioned that the process of photodegradation of inorganic nitrogen in water would generate highly reactive ·OH and O2 − and other reactive oxygen species, which have photocatalytic ability. Inorganic nitrogen ions can induce a series of REDOX reactions, mainly containing NH4 + oxidation and NO3 − reduction (Formulas (6-10)). However, the specific mechanism is still not yet confirmed, and it needs further research. 2 NO3-N and NO2-N were detected as the photocatalytic degradation products of ammonia nitrogen wastewater as the following Figure 8. After 300 min of photocatalytic reaction using La/Fe/TiO2 as the photocatalyst, the concentration of ammonia nitrogen reached to 34.96 mg/L by the initial concentration of 100.67 mg/L and the conversion rate was 64.6%. During the degradation process, 9.56 mg/L of NO3-N and 2.07 mg/L of NO2-N were generated. Considering the escape free ammonia and adsorption part onto the catalyst's surface, it is proposed that at least 20% of ammonia nitrogen was converted to N2 according to the mass balance of the total nitrogen [44].

Conclusions
La-Fe-codoped catalyst demonstrates better physical chemical properties in photocatalytic activity than pure TiO2: first of all, the doped catalysts were in anatase phase while the pure TiO2 was in rutile phase; second, the composites possessed strong visible-light-response ability; third, La/Fe/TiO2 had larger specific surface area and more regular shape in morphology. Furthermore, the doped catalysts indicated higher photocatalytic degradation ability to ammonia nitrogen wastewater: the removal rate of ammonia nitrogen reached to 78.3% at the conditions of pH 9.9, 100.67 mg/L of ammonia nitrogen, 1 g/L of catalyst, and 2 mmol/L of H2O2. Besides, the common inorganic ions in water all inhibited the degradation of ammonia nitrogen. At last, it is proposed that there at least 20% of ammonia nitrogen was converted to nitrogen gas during the photodegradation process with 64.6% removal efficiency of ammonia nitrogen.