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Preparation, Photocatalytic Activity, and Mechanism of Nano-TiO Co-Doped with Nitrogen and Iron (III)
2

Ye Cong, Jinlong Zhang, Feng Chen, Masakazu Anpo, and Dannong He
J. Phys. Chem. C, 2007, 111 (28), 10618-10623• DOI: 10.1021/jp0727493 • Publication Date (Web): 20 June 2007 Downloaded from http://pubs.acs.org on April 22, 2009

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By analyzing the structures and photocatalytic activities of the undoped and nitrogen and/or Fe3+-doped TiO2 under ultraviolet and visible light irradiation. Therefore. improving the utilization efficiency of the solar energy. it is an important and challenging issue to develop new TiO2 photocatalytic system with enhanced activities under both UV and visible light irradiation compared with the bare TiO2. and V have been employed to tune the electronic structure and enhanced the photocatalytic activity of the titanium dioxide. Osaka 599-8531. 245 Jiachuan Road.*.‡ and Dannong He§ Lab for AdVanced Materials and Institute of Fine Chemicals. ion used. Phys. 2007. XPS.† Masakazu Anpo.1-3 However. doped with 21 kinds of metal ions prepared by sol-gel method. the co-doping can also promote the separation of the photogenerated electrons and holes to accelerate the transmission of photocurrent carrier. Introduction One of the most intriguing application areas of titanium dioxide is the photocatalytic activity for environment protection since it can decompose a large number of organic and inorganic pollutants. Osaka Prefecture UniVersity. the probable mechanism of co-doped particles was investigated. 10618-10623 Preparation. while the UV photocatalytic activities are seldom studied. few reports are published on TiO2 photocatalyst co-doped with nitrogen and iron (III) for photo-oxidative degradation of organic pollutants. 1. some theoretical calculations have also been performed to suggest that anion doping of TiO2 has considerable effects on the band gap alteration.cn. Co. Graduate School of Engineering. Shanghai 200237.9 Anpo and co-worders suggested that the injected metal ions isomorphicaly replaced Ti4+ ions in TiO2 and decreased the band gap to enable absorb the visible light. The factors influencing the photocatalytic activity and the probable mechanism of co-doped nanoTiO2 are investigated. NOx and the decomposition of dyes such as methylene blue. many efforts have been attempted by modification titanium dioxide with nonmetals. Unfortunately. C. and Mechanism of Nano-TiO2 Co-Doped with Nitrogen and Iron (III) Ye Cong.1021/jp0727493 CCC: $37. and F. we prepare nanocrystalline TiO2 photocatalysts co-doped with nitrogen and iron (III) by homogeneous precipitation-hydrothermal method. the degradation efficiencies of which were improved by 75% and 5% under visible and ultraviolet irradiation. The co-operation of the nitrogen and Fe3+ ion leads to the much narrowing of the band gap and greatly improves the photocatalytic activity in the visible light region.13. China ReceiVed: April 9. have reported that TiO2. The prepared photocatalysts manifest higher photocatalytic activities for photodegradation of rhodamine B under both ultraviolet and visible light irradiation. Therefore. exhibited various colors depending on the * Corresponding author. In Final Form: May 14. Raman. Sakai. The structure and properties of the co-doped were studied by XRD. it is a challenging issue to develop a photocatalyst with higher photocatalytic activity under both ultraviolet and visible light irradiation. Choi et al. It is well-known that nitrogen doping can improve the phtocatalytic activity of titania in the visible region. and UV-diffuse reflectance spectra. E-mail: jlzhang@ecust. Chem. respectively. acetaldehyde. Here. Tel: +86-21-64252062. 130 Meilong Road. Mo. C 2007. It is presumed that the nitrogen and Fe3+ ion doping induced the formation of new states closed to the valence band and conduction band. S. N.† Jinlong Zhang. respectively. To the best of our knowledge. and Shanghai National Engineering Research Center for Nanotechnology. Fax: +86-21-64252062.11-16 Furthermore. 10. such as B. gaseous 2-propanol. This method can avoid the agglomeration and growth of particles in the process of higher temperature calcinations. ethanol.10618 J. 1-1 Gakuen-cho. 2007 Nanoparticles of titanium dioxide co-doped with nitrogen and iron (III) were first prepared using the homogeneous precipitation-hydrothermal method. Cr. China. East China UniVersity of Science and Technology. Department of Applied Chemistry.4-8 It has been hypothesized that the advantages of the doping of the metal ion in TiO2 are the temporary trapping of the photogenerated charge carriers by the dopants and the inhibition of their recombination during migration from inside of the material to the surface or the enhanced adsorption of the goal pollutants onto the doping ion surface sites. The photocatalyst co-doped with nitrogen and 0. because of the wide band gap of titanium dioxide. Meanwhile. 111. Some metal elements such as Fe. § Shanghai National Engineering Research Center for Nanotechnology. Impurity doping is one of the typical approaches to extend the spectral response of the titanium dioxide to visible light region.edu. the UV photocatalytic activities are relatively low.† Feng Chen. † East China University of Science and Technology. Photocatalytic Activity. Shanghai 200237. so as to efficiently extend photoresponse from UV to visible light region.5% Fe3+ shows the best photocatalytic activity. Japan. in many cases.00 © 2007 American Chemical Society Published on Web 06/20/2007 . its practical application is inhibited for the low photon utilization efficiency and need of an ultraviolet excitation source which accounts for only small fraction of the solar light (3-5%). compared with the pure titania.10 Recently. FL. ‡ Osaka Prefecture University.17 The success in nitrogen doping and increasing the photocatalytic activity of TiO2 in visible light region provides good opportunities for extensive applications such as oxidation of CO.

3.2. The shift of binding energy due to relative surface charging was corrected using the C1s level at 285. 2. We think all the iron ions were incorporated into the structures of titania and replaced titanium ion or located at interstitial site. C. It can be seen from Figure 1 b that the samples after doping with nitrogen show trace amount of brookite phase.1%. (e. The crystallite sizes of samples were calculated using the Debye-Scherrer equation and the values are given in Table 1. 111. The product was kept in infrared drying oven to dry overnight and the nitrogen and Fe3+-co-doped TiO2 photocatalysts were obtained. 0. UV irradiation was carried out using a 300 W high-pressure mercury lamp. Experimental Section 2. The formed gel precipitation was aging for 24 h to completely hydrolyze. The instrument employed for XPS studies was Perkin-Elmer PHI 5000C ESCA System with Al KR radiation operated at 250 W. (d.5.Nano-TiO2 Co-Doped with Nitrogen and Iron (III) 2. the suspensions were magnetically stirred in dark for 30 min to ensure the establishment of an adsorption/ desorption equilibrium. using BaSO4 as reflectance sample. The Raman spectra were recorded on an inVia + Reflex spectrometer equipped with an optical microscope at room temperature.0 eV as an internal standard.22µm membrane filter to remove the particles. (b. sampled. Preparation of Samples. The Fe3+-doping concentration (x) was chosen as 0. (f. Chem. The crystallite size of all prepared samples is about 10-12 nm. about 4 mL aliquots were J. with R-silicon (99. λ ) 1.05 g catalyst powders were added into 50 mL of the above rhodamine B solution in quartz tube. Structures and Properties of Photocatalysts. Results and Discussion 3. a total of 0.0%. e′) 1.1. The UV-visible absorbance spectra were obtained for the dry-pressed disk samples using a Scan UV-visible spectrophotometer (Varian. Moreover. The shortwavelength components (λ< 420 nm) of the light were cut off using a glass optical filter.05%. The electron paramagnetic resonance (EPR) spectra were recorded at 298 K using a Bruker AVANCE 500 electron paramagnetic resonance spectrometer. g′) 2. For excitation.xFe-TiO2. c′) 0. b′) 0. operated at 40 kV and 100 mA. and 2.5.5%. For a typical photocatalytic experiment. At given time intervals. centrifuged. 2. 2007 10619 Figure 1. 28.0. Given the ammonium chloride was used as the nitrogen source. the 514.0. The obtained corresponding concentration photocatalysts were denoted as xFe-TiO2 and N. on the sample under the microscope. the irradiation wavelength of which was predominated at 365 nm. A 1000 W halogen lamp was used as the visible light source of the homemade photoreactor.5406 Å).18 It is noteworthy that no iron oxide or FexTiOy peak could be observed in the XRD spectra. Phys. The filtrates were analyzed by recording variations in the absorption in UV-visible spectra of rhodamine B using a Cary 100 Ultraviolet-visible spectrometer.5%.5 nm line from an Ar+ ion laser (Spectra Physics) was focused.0 mL tetrabutyltitanate was mixed with 25 mL absolute alcohol. which indicates the post hydrothermal can effectively prompt . the XRD patterns of xFe-TiO2 and N-xFe-TiO2 with different Fe3+-doping concentration are provided. Prior to irradiation. which was the mole percentage of Fe3+ in the theoretical titania powder.0%. Cary 500) equipped with an integrating sphere assembly. this response is reasonable because a high chloride concentration promotes the crystallization of brookite. The above suspensions were kept under constant air-equilibrated conditions before and during the irradiation.9999%) as a standard for the instrumental line broading. with an analyzing spot about 1 µm. A desired amount of solid ferric nitrate and 17.1. Photocatalytic Activity Measurements. a′) 0. Characterization Methods. (g. Ammonium chloride was used as a nitrogen source.1. In order to diminishing the experimental error. No. In Figure 1. Vol. 1. (c. and filtered through a 0. surrounded with cool water at the outer wall through a quartz jacket. the precipitate at the bottom of the autoclave was obtained and washed with ethanol and deionized water several times. f′) 1. X-ray diffraction patterns of xFe-TiO2 (a) and N-xFeTiO2 (b) with different Fe3+-doping concentration: (a. the photocatalytic tests of xFe-TiO2 and N-xFe-TiO2 for the same Fe 3+-doping concentration are parallel determined at the same time and conditions. The major crystalline phase detected in all samples is anatase. The photocatalytic activity was evaluated by measuring the decomposition of the distilled water solution of rhodamine B (with a concentration of 20 mg/L) under UV and visible light irradiation. After the autoclave was cooled to room temperature. 1. d′) 0. X-ray diffraction (XRD) patterns of all samples were collected in the range 20-80° (2θ) using Rigaku D/MAX 2550 diffractometer (Cu KR radiation.3. The photoluminescence (PL) spectra were measured through fluorospectrophotometer (Cary Eclipse) by using 280 nm line of Xe lamp as excitation source at room temperature. The mixture was slowly dropped into a solution of ammonium chloride in water with continuously stirring. The crystallite size was estimated by applying the Scherrer equation to the fwhm of the (101) peak of anatase and the (110) peak of rutile. Tetrabutyltitanate and ferric nitrate were used as starting materials. Then the obtained mixture was changed into 100 mL Teflonlined stainless steel autoclave and then heated under 180 °C for 12 h. we repeated experiment at least three times for the same sample and chose the mean value in our experiment.

six fundamental transitions are expected in the Raman spectrum of anatase. It is because that the surrounding environment of Fe3+ in the TiO2 lattice is different for the nitrogen and iron co-doped samples since there is nitrogen atoms existed around the Fe3+. while Fe2+ can not. Furthermore. it can be evidently seen that the intensities of this peak are dramatically increased and its widths are broadened after nitrogen doping. which is corresponding to the XRD results. Furthermore. Raman peak at about 146 cm-1 is observed for all the samples. From a measurement of the maximum of the low-frequency Raman band. In addition. Vol.5%Fe-TiO2. and 640 cm-1 (Eg) are present in the spectra for all samples. However. it is possible to determine the nanoparticle size since the particle size can cause large shifts in the location of the scattered Raman peaks and their widths. Furthermore.22 Both the substitutional and interstitial nitrogen could affect the electronic band structure of TiO2 and improve the photocatalytic activity in the visible light region. 2007 TABLE 1: The Diameter of the Crystallites of Anantase Phase for xFe-TiO2 and N-xFe-TiO2 with Different Fe3+-Doping Concentration no. which can be attributed to Fe3+ substituted Ti4+ in the TiO2 lattice.5%Fe-TiO2 is broaden and the intensity is higher than that of N-0.98 10. the effect of nitrogen on the paramagnetic signal of Fe3+ is not evident.15 N-xFe-TiO2 (nm) 9.01% are detectable) and can give valuable information about the lattice site. At room temperature. Phys.992. and 639 cm-1) are Raman-active.5%Fe-TiO2 (Figure 4c) and N-0. when the iron doping concentration increases. The XPS spectra for the N1s region of N-TiO2 and N-0. 111. Fe3+ can easily give the EPR signals. 516 cm-1 (A1g). and thus. This peak can be assigned to substitutional nitrogen replaced one O atom of the TiO2 lattice or the interstitial nitrogen bound to one lattice oxygen and formed a NO species. No. The main peak appears at about 399 eV. 28. which indicates that anatase TiO2 nanoparticles are the predominant species.21 Consequently. which is attributed to the main Eg anatase vibration mode.5%Fe-TiO2.52 9. the phases are easily distinguishable. 197. The information obtained from EPR may provide detailed description both of the nature of the species and their co-ordination symmetries in the solid.80 9.5%Fe-TiO2. we conclude that the iron ion has been incorporated into the lattice of titania. vibration peaks at 199 cm-1 (Eg. and therefore.00 1. which is consistent with the results of XRD patterns. there are no signal of paramagnetic species. There is some difference between the 0. crystallization and inhibit the grain growth compared with the high temperature annealing. C.85 11. and Eg (144.5%Fe-TiO2 (Figure 4d).23 11. Chem. B1g (399 cm-1).10 0.19 Figure 2 shows the Raman spectra of different samples. which could probably influence the characteristics of the nitrogen state.44 Cong et al. the XPS spectra for the N 1s region of nitrogen doped and nitrogen and iron codoped titania are presented.6.59 10. which is a highly sensitive technique for examining paramagnetic species (levels of Fe <0. 399 cm-1 (B1g). By analyzing the preparation methods and peak characterizations in the XPS spectra of the nitrogen-doped titania. compared the lowest frequency peak at 146 cm-1 of the different samples.05 0. In Figure 3. Raman spectroscopy is a powerful technique for the investigation of various phases of titanium dioxide. the crystallite size of the samples after nitrogen doping is smaller than that of the undoped samples and corresponding concentration Fe3+-doped samples.63 9. However. provided. The modes A1g (519 cm-1). the assignment of the XPS peak of N1s has still been under debate.8 Therefore. For the undoped TiO2 and N-TiO2 (Figure 4 a.50 2. the peak position may be different from the literatures. Figure 2. Up to now.82 10. Electron paramagnetic resonance (EPR) spectroscopy has been used to study the iron-doped titania system both for laboratory prepared samples and commercial pigments. It indicates that the crystallinity is enhanced and the particle size is decreased.59 11.00 0. It is well-known that transition-metal ions are generally paramagnetic due to their partially filled d orbits. and controversial hypotheses have been Figure 3. it can be seen that there is no significant difference between the N-TiO2 and N-0.20.00 xFe-TiO2 (nm) 10.18 15. Raman spectra of different samples. there is no peak attributed to iron oxide observed.26 10. It can be observed that the signal of 0. It is thought that nitrogen doping prolongs the crystallization of anatase and retards the transformation of amorphous titania to anatase since the crystallinity of nitrogen doped samples is lower than that of undoped samples. due to its very short relaxation time.10620 J. which is probably due to that the relative concentration of nitrogen around the . the nitrogen source is different. all samples after iron doping show the obvious signal at g ) 1.b). Since the preparation methods and conditions largely affect nitrogen XPS spectral features. we think that the peak position lies in the range of 397401 eV is much reasonable to the one when using the wet chemical method.50 1.14 12. This technique is capable of elucidating the photocatalyst structural complexity as peaks from each material are clearly separated in frequency. 1 2 3 4 5 6 7 x (Fe mol %) 0. Moreover. namely the quantum size confinement effect. weak).

energy level of the dopant within the TiO2 lattice. For the xFe-TiO2 photocatalysts.Nano-TiO2 Co-Doped with Nitrogen and Iron (III) J. 2007 10621 Figure 4. It is significant to point out that the photodegradation activities of TiO2 co-doped with nitrogen and Fe3+ ion are much higher than that of doped with the nitrogen or Fe3+ ion with the corresponding concentration alone. same iron for the N-1. the photodecomposition activities of RB over xFe-TiO2 and N-xFe-TiO2 with different Fe3+-doping concentration under UV light irradiation for 2 h are presented. The photocatalytic activity of rhodamine B (RB) was investigated by determining the remaining concentration of RB at various time intervals. respectively. Vol. The Fe3+ dopant can serve as a charge traps retarding the electron-hole combination rate and enhancing the interfacial charge transfer to degrade the RB within the suitable concentration range of dopant (lower than 0. (d) N-0. Fe3+ doping becomes detrimental when the doping concentration is higher than the optimal value.5 atom %). When the dopant concentration is too high. The electronic transitions from the valence band to dopant level or from the dopant level to the conduction band can effectively red shift the band edge adsorption threshold. all the doped samples show the much higher photodecomposition activity compared with the pure TiO2.5 atom % for the maximum photodecomposition of RB. the band gap of titania becomes narrowing compared to the undoped and doped samples with nitrogen or Fe3+ alone. Since the starting absorption edge of co-doped sample shifts to the lower energy. EPR spectra of (a) TiO2.0%Fe-TiO2 measured at room temperature. Photocatalytic Activities of Photocatalysts. The red shift of the absorption edge in Fe3+-doped titania has been attributed to the charge-transfer transition between the iron ion d electrons and the TiO2 conduction or valence band. (c) 0.5%Fe-TiO2.5%. 111. 28. No. The optimal Fe3+-doping concentration is 0. Chem. the recombination rate will increase because the distance between trapping sites in a particle decreases.8 Furthermore.0%Fe-TiO2 is decreased compared with the N-0. 3. of Figure 5.5 atom %. When the Fe3+-doping concentration is less than 0.9 Therefore. Figure 5.23 It has been reported that metal doping could form a dopant energy level within the band gap of TiO2. UV-vis diffuse reflectance spectra of xFe-TiO2 and N-xFeTiO2 with different Fe3+ doping concentration are presented in panels a and b. With the increasing of Fe3+-doping concentration. The UV-diffuse reflectance spectra of xFe-TiO2 (a) and N-xFe-TiO2 (b) with different Fe3+-doping concentrations. Phys. the absorbance increases. and (f) N-1. the efficiencies of the doped titania are changed. doping concentration. the absorption of samples co-doped with nitrogen and Fe3+ ion is abruptly stronger than that of the Fe3+-doped samples with the corresponding doping concentration of Fe3+. (b) N-TiO2. It is apparent that the diffuse reflectance spectra of all the samples doped with nitrogen and/or Fe3+ have extended a red shift and increased absorbance in the visible range. Photodecompositon activity of RB over xFe-TiO2 and N-xFe-TiO2 with different Fe3+-doping concentrations under visible light irradiation for 4 h. and the distribution of the dopant in the particle. Since the metal ion dopant can act as a mediator of interfacial charge transfer or as a recombination center. the doping concentration has a optimal value.5%Fe-TiO2. such as preparation method. Figure 6. The probably mechanism is discussed in the following part. Many factors can affect the efficiency of photodecomposition. (e) 1.2.0%Fe-TiO2.5%Fe-TiO2. the photocatalytic activities of the Fe3+-doped titania are slightly higher than . In Figure 7. Figure 6 shows the photodecomposition activity of RB over xFe-TiO2 and N-xFe-TiO2 with different Fe3+ doping concentration under visible light irradiation for 4 h after the dark adsorption for 30 min. In Figure 6. C. the photocatalytic activities increase with the Fe3+-doping concentration when the concentration is below 0.

Chem. 111. Therefore. which all could decrease the band gap of TiO2 and absorb the visible light. Considering the effects of nitrogen doping and iron ions doping and the differences of photocatalytic activities between the nitrogen and/or Fe3+-doped titania. Figure 9.5%. the recombination of electrons and holes (process E) are relatively faster. In the ultraviolet irradiation.5% Fe3+ ions titania is relatively faster in the ultraviolet irradiation. the co-doping with nitrogen and Fe3+ induces the band gap of TiO2 much narrowing. i. which is probably the reason of the photocatalytic activity decreasing. Phys. No. although the codoping with nitrogen and iron ions narrows the band gap of the titania. another reason of the photocatalytic activities of nitrogen doping in the ultraviolet decrease may be the unsuitable of the nitrogen doping concentration. it can be deduced that the recombination efficiency of the nitrogen and 0. the recombination of the electrons and holes may be faster compared with the pure titania and become the controllable procedure for the . the probably mechanism of the improvement of the photocatalytic activity in visible light region by co-doping with nitrogen and Fe3+ ion is due to the band gap narrowing and the enhancement of the utilization efficiency of solar energy. while that of the nitrogen and Fe3+co-doped titania are lower than that of the Fe3+-doped alone. which is not the optimal value.5%Fe-TiO2 and (b) N-0. 2007 Cong et al. Anpo and co-workers have reported that in the metal ion-implanted TiO2 the overlap of the conduction band due to Ti (d orbital) of TiO2 and the metal (d orbital) orbital of the implanted metal ions could decrease the band gap of TiO2 to absorb the visible light.Probable Mechanism Discussion. Photoluminescence emission spectra for (a) 0. Therefore. In a word. respectively. which have been widely used to investigate the efficiency of charge carrier trapping. respectively. the process A cannot occur.25. C.10622 J. the electron can be excited from the N impurity level to the Fe3+ impurity level (process B) or from the N impurity level to the conduction band (process C) or from the valence band to the Fe3+ impurity level (process D).3.5% iron ions doped TiO2. When the Fe3+-doping concentration increases higher than 0. that of the undoped titania. The suitable concentration range of Fe ion can trap the photogenerated electron. the lower PL intensity of the doped sample indicates a lower recombination rate. In addition. Photodecomposition activity of RB over xFe-TiO2 and N-xFe-TiO2 with different Fe3+-doping concentration under UV light irradiation for 2 h.5%Fe-TiO2 (a) and N-0.. Further experiments are needed. After nitrogen and Fe3+ doping. It can be seen that the PL emission intensity of the nitrogen and 0. in the visible light irradiation. 3. We presume that there are electrons excited from the valence band to the conduction band (process A) for the pure titania under the ultraviolet irradiation. On the other hand. and transfer and to understand the fate of electron-hole pairs in semiconductor particles since PL emission results from the recombination of free carriers. the photocatalytic activities of Fe3+-doped titania decrease abruptly. which enhances the utilization efficiency of photogenerated electron and hole. On the one hand. Excitation wavelength ) 280 nm.5%Fe-TiO2 (b).24 Therefore. Vol. while that of the codoped catalysts higher than that of the Fe3+-doped alone.5% iron ions doped TiO2 is higher than that of the 0. the effects of doping on the process of photodecomposition may be different. It can be supported by the PL emission spectra. the co-doping of nitrogen and Fe3+ ion inhibits the recombination of the photogenerated electron and hole. the electron cannot be excited from the valence band to the conduction band for the pure titania. When there are nitrogen ions existed surrounding the Fe3+.26 Figure 9 shows the PL spectra of the 0. migration.5%Fe-TiO2 powders measured at room temperature. Because the PL emission is the result of the recombination of excited electrons and holes. Therefore the quantity of the photoinduced electrons and holes is much higher than that of the pure titania and the nitrogen or Fe3+-doped titania. In a word. Figure 8. The co-operation of the nitrogen and Fe3+ ion leads to the much narrowing of the band gap and greatly improves the photocatalytic activity in the visible light region. As illustrated in Figure 8. 28. Figure 7. it is generally accepted that nitrogen doping can form a new states lie just above the valence band for the substitutional nitrogen or lie higher in the gap. while the nitrogen can trap part of photogenerated holes. the nitrogen and Fe3+ ion doping induced the formation of new states closed to the valence band and conduction band. The schematic diagram of mechanism of the nitrogen and Fe3+ co-doping.24 Furthermore.e. the probable schematic diagram is proposed. It can also be testified by the UV-vis diffuse spectra (Figure 5). the recombination possibility of electrons and holes is enhanced since the nitrogen and Fe3+ could trap holes and electrons.

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