Kaliyamoorthy
Selvam
and
Meenakshisundaram
Swaminathan
*
Department of Chemistry, Annamalai University, Annamalainagar 608 002, India. E-mail: chemres50@gmail.com; Fax: +91 4144 225072
First published on 9th February 2012
N-Doped TiO2 using a new nitrogen precursor hydrazine hydrate was synthesized by a simple wet method. This photocatalyst was characterized by X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) surface area, high resolution transmission electron microscopy (HR-TEM), UV-Vis diffused reflectance spectra (DRS), photoluminescence (PL) and X-ray photoelectron spectroscopy (XPS). N-Doping does not change the phase of TiO2. It is found that the size of N-TiO2 is 15.6 nm with 134.72 m² g−1 surface area. XPS analysis reveals the presence of anionic nitrogen in TiO2 as O–Ti–N. Substitution of N in place of oxygen in the TiO2 lattice causes a decrease in oxygen vacancies which inhibits the recombination of electron–hole pairs. This catalyst was used for the selective one-pot synthesis of quinaldines from nitrobenzenes in ethanol under UV and visible light. N-TiO2 on irradiation induces a combined redox reaction with nitrobenzene and alcohol and this is followed by condensation-cyclization of aniline with oxidation products to give quinaldines. N-Doped TiO2 is found to be more efficient than metal doped TiO2 in quinaldine synthesis under visible light. Higher activity of the N-TiO2 could be attributed to its stronger absorbance of visible light.
Many researchers have shown that doping nitrogen into TiO2 to form TiO2–xNx can efficiently shift the optical response to the visible spectral range.4–6 The synthesis of N-doped TiO2 nanophotocatalysts can be achieved by a sol–gel method,7 hydrothermal method,8 solvothermal method,9 chemical vapour deposition,10 emulsion precipitation,11 electrical oxidation,12 sputtering, ion implantation,13 spray pyrolysis5 and oxidation of TiN.6
Most of the above methods need a higher temperature or complicated and expensive equipment. Therefore, it is promising to develop a simple and lower temperature method for the preparation of the nitrogen-doped TiO2.
Li et al. reported the wet method for the synthesis of excellent visible-light responsive (from 400 to 550 nm) TiO2–xNx photocatalysts at low temperature.14 This catalyst was prepared by treating self-made amorphous TiO2 powder with hydrazine hydrate at 110 °C. On the other hand, the solution combustion technique (CS) has been extensively used for the synthesis of nanotitania [CS–TiO2].15–17 TiO2 obtained by the CS method is nanosized (8–12 nm) with high surface area. Therefore, nitrogen-doping on CS–TiO2 using hydrazine hydrate is expected to produce an efficient photocatalyst in UV and visible light. This nitrogen-doping method is very simple and does not need calcination at high temperature. However, N-TiO2 was mostly used for photodegradation of organic pollutants.18,19
Synthetic methods reported by Skraup, Doebner–Von Miller, Friedlander, and Combes have been developed for the preparation of quinolines.20–22 But many of these methods are not fully satisfactory with regard to operational simplicity, cost of the reagent and isolated yield. Photocatalytic synthesis of quinoline derivatives from nitrobenzene using TiO2, metal doped TiO2 and others had been reported earlier.23–25 In the present study, an attempt has been made for the preparation of N-doped TiO2 by a simple wet method using hydrazine hydrate with CS–TiO2. The efficiency of the N-TiO2 photocatalyst has been evaluated by the photocatalytic synthesis of quinaldines from nitrobenzenes.
CS–TiO2 was dipped in hydrazine hydrate (80%) for 12 h, then filtered and dried at 110 °C for 3 h in air. Finally, the yellow nitrogen-doped TiO2 powder was formed. In the drying process, during evaporation, a glow was detected on the surface of the powder for a moment. Then the catalyst turned yellow.
D = Kλ/β cos θ |
Where D is the crystal size of the catalyst, λ is the X-ray wavelength (0.154 nm), β is the full width half maximum of the catalyst, K = 0.89 and θ is the diffraction angle.
The phase formation, particle size, surface morphology and crystallinity of pure and loaded catalysts were examined using transmission electron microscope (TEM) (Model JEOL TEM-3010) operated at 300 keV. The samples for TEM analysis were prepared by dispersing the catalysts in ethanol under sonication and depositing on a copper grid. High resolution TEM (HR-TEM) measurements were carried out using a JEOL-JEM-2010 UHR instrument operated at an acceleration voltage of 200 kV with a lattice image resolution of 0.14 nm. X-Ray photoelectron spectra (XPS) of the catalysts were recorded in an ESCA-3 Mark II spectrometer (VG Scientific Ltd., England) using Al Kα (1486.6 eV) radiation as the source. The spectra were referenced to the binding energy of C1s (285 eV).
The DRS of all the catalysts were recorded in a Shimadzu UV 2450 model UV-visible spectrophotometer in the range 800–190 nm equipped with an integrating sphere and using powdered BaSO4 as a reference.
The specific surface areas of the catalysts were determined using a Micromeritics ASAP 2020 sorption analyzer. The samples were degassed at 423 K for 12 h and analysis was performed at 77 K with N2 gas as the adsorbate. The Brunauer–Emmett–Teller (BET) multipoint method least-square fit provided the specific surface area.
Photoluminescence (PL) spectra at room temperature were recorded using a Perkin Elmer LS 55 fluorescence spectrometer. The nanoparticles were dispersed in carbon tetrachloride and excited using light of wavelength 300 nm.
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Fig. 1 XRD patterns from (a) bare TiO2, (b) TiO2-P25 and (c) N-TiO2. |
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Fig. 2 Diffuse reflectance spectra of (a) bare TiO2, (b) N-TiO2 and (c) TiO2-P25. |
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Fig. 3 Photoluminescence spectra of (a) bare TiO2, (b) TiO2-P25 and (c) N-TiO2. |
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Fig. 4 HR-TEM analysis: (a, b) images at two different regions of N-TiO2, (c) SAED pattern of N-TiO2, (d) lattice fringes of N-TiO2 and (e) particle size distribution of N-TiO2. |
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Fig. 5 X-Ray photoelectron spectra of N-TiO2: (a) survey spectrum, (b) Ti2p peak, (c) O1s peak, (d) N1s peak and (e) C peak. |
N-TiO2 shows a single peak at 398.1 eV (Fig. 5d) for nitrogen N1s core level. Nitrogen from simple chemisorbed nitrogen or TiN should appear at ≤397.5 eV and nitrogen in NO or NO2 type species appear above 400 eV.31–33 Hence this N1s peak at 398.1 eV can be attributed to the anionic N in O–Ti–N linkages. Further the direct interaction between N and O in the lattice is ruled out as this interaction will increase the BE of the N1s level. It is also supported by the low BE of Ti2p of 458.1 eV compared to that of pure TiO2 (459.3 eV). From the above observations it can be concluded that the peak observed in the present study at 398.1eV is due to the N− anion incorporated in the TiO2 as a O–Ti–N structural feature.
Fig. 5b shows that the high intense peaks of Ti2p3/2 and Ti2p1/2 core levels of N-TiO2 appear at 458.1 and 463.1 eV, respectively. But with pure TiO2, binding energy peaks of Ti2p3/2 and Ti2p1/2 were reported at 459.3 and 465.0 eV, respectively.34 This reveals that nitrogen doping decreases binding energies of Ti2p3/2 and Ti2p1/2 peaks. Lower binding of Ti2p in N-TiO2 indicates the electronic interaction between Ti and N− anions, which can cause partial electron transformation from N to Ti. Electron density on Ti increases due to the lower electronegativity of nitrogen compared to oxygen. Earlier Miao et al. also assigned lower binding energy peaks to TiO2–xNx.35 This further confirms that nitrogen is incorporated into the lattice and substitutes for oxygen.
It can be seen from Fig. 5c that the O1s spectra of the N-doped TiO2 consisted of two peaks: one was centered at 529.7 eV and the other was centered at 531.6 eV, which is ascribed to nitrogen dopant. This indicates the presence of another type of oxygen due to the more covalent nature of N-TiO2. The carbon peak is attributed to the residual carbon from the sample and adventitious hydrocarbon from XPS instrument itself (Fig. 5e).
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Fig. 6 (a) N2 adsorption–desorption isotherms of N-TiO2 and (b) its pore size distribution. |
The changes in the concentrations of nitrobenzene, aniline and quinaldine during the photocatalytic reaction with TiO2, TiO2-P25 and N-TiO2 were determined at different times (Fig. 7). With TiO2-P25 and bare TiO2 (Fig. 7a and 7b), 6 h photoirradiation of nitrobenzene gave only 55 and 60% yield of the product quinaldine, respectively. In contrast, 70% yield of quinaldine was obtained in 5 h with N-TiO2 (Fig. 7c). This indicates that N-TiO2 promotes rapid and selective quinaldine production. Based on the results, it is obvious that N-TiO2 has higher photocatalytic activity compared with pure TiO2, which is ascribed to the N dopant. This is consistent with the analytical results. According to the XRD analysis, the N dopant of TiO2 decreased the crystalline size of TiO2 which resulted in the increase of surface area of the TiO2 from 74 to 134.0 m² g−1. N2 adsorption–desorption isotherms indicate the mesoporous nature of N-TiO2. Higher surface area and mesoporous structure increase the photocatalytic activity of N-TiO2. Furthermore the entry of N into the TiO2 lattice suppressed the particle growth and consequently caused a decrease of oxygen vacancies, which minimized the electron–hole recombination during the photocatalytic synthesis of quinaldines.
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Fig. 7 Time-dependent change in the concentrations of nitrobenzene and products during photoirradiation of nitrobenzene with (a) TiO2, (b) TiO2-P25 and (c) N-TiO2. [Nitrobenzene] = 25 mM, N2 flow rate = 6.1 mL s−1, I = 1.381 × 10−6 einstein L−1 s−1, irradiation time = 5/6 h. |
GC-MS chromatograms recorded at different reaction times of the photocatalytic conversion of nitrobenzene in ethanol are presented in Fig. 8. GC-MS chromatograms reveal the formation of nitrosobenzene, aniline, N-hydroxyaniline, N-(propan-2-yl)aniline, 2-methyl-1,2,3,4-tetrahydroquinolin-4-yl(phenyl)amine during the quinaldine formation. The formation of byproducts, aniline and 2-methyl-1,2,3,4-tetrahydroquinoline after 6 h is also indicated by the GC-MS chromatogram. Very recently, we reported a similar reaction with a plausible reaction mechanism of the formation of quinaldine from nitrobenzene catalyzed by Au–TiO2.25 Since the intermediates formed are same, this reaction also follows the same mechanism. To find out the optimum conditions for maximum efficiency of this reaction, various experiments under different conditions were carried out.
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Fig. 8 GC-MS chromatograms at different reaction times for the photocatalytic conversion of nitrobenzene with N-TiO2. |
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Fig. 9 Percentage of quinaldine formed under different catalyst dosage. [Nitrobenzene] = 25 mM, N2 flow rate = 6.1 mL s−1, I = 1.381 × 10−6 einstein L−1 s−1, irradiation time = 5 h. |
Run | Concentration of nitrobenzene (mM) | % of quinaldine |
---|---|---|
a Catalyst suspended = 50 mg/25 mL, N2 flow rate = 6.1 mL s−1, I = 1.381 × 10−6 einstein L−1 s−1, irradiation time = 5h. | ||
1 | 15 | 78 |
2 | 25 | 70 |
3 | 35 | 56 |
4 | 45 | 37 |
Reactant | Products yield (%) | Byproduct (%) | Conversion |
---|---|---|---|
a All reactions were performed with a 25 mM alcoholic solution of a reactant 50 mg of N-TiO2 suspension, I = 1.381 × 10−6 einstein L−1 s−1, irradiation time = 5 h. | |||
Nitrobenzene | Quinaldine (70) | 29 | 99 |
3-Nitrotoluene | 2,7-Dimethylquinoline (80) | 18 | 98 |
4-Nitrotoluene | 2,6-Dimethylquinoline (75) | 23 | 98 |
4-Methoxy-nitrobenzene | 6-Methoxy-2-methylquinoline (70) | 26 | 96 |
3-Methoxy-nitrobenzene | 7-Methoxy-2-methylquinoline (72) | 22 | 94 |
3,5-Dimethyl-nitrobenzene | 2,5,7-Trimethylquinoline (66) | 19 | 85 |
4-Chloro-nitrobenzene | 6-Chloro-2-methylquinoline (36) | 64 | 99 |
4-Fluoro- nitrobenzene | 6-Fluoro-2-methylquinoline (20) | 79 | 99 |
It seems that the electron releasing group at the para position inhibits the condensation of the amino group with aldehyde. This is also revealed by 70% quinaldine formation by 4-methoxynitrobenzene which has a strong electron releasing group at the p-position. In the case of 3,5-dimethylnitrobenzene, the cyclization reaction is hindered due to the steric effect and this decreases the product yield (66%) when compared to 3-nitrotoluene (80%). In the case of 4-chloro- and 4-fluoronitrobenzenes, the yield of quinaldines was very low. This is attributed to photoinduced dehalogenation. Dehalogenated anilines have been identified in the GC-MS analysis.
Earlier it was reported that the irradiation of nitrobenzene (2 mmol) and TiO2 (0.5 g) in nitrogen saturated ethanol solution for 8–12 h gave ethoxy-tetrahydroquinolines as the major product.23 We obtained a different product with continues purging of nitrogen during the reaction. Our results reveal that of N-TiO2 has good oxidizing power under these experimental conditions.
Run | Additives | % of quinaldine |
---|---|---|
a [Nitrobenzene] = 25 mM, catalyst suspended = 50 mg/25 mL, N2 flow rate = 6.1 mL s−1, I = 1.381 × 10−6 einstein L−1 s−1, irradiation time = 5 h. | ||
1 | Without additive | 70 |
2 | KI | 76 |
3 | KBr | 71 |
4 | NaI | 84 |
5 | NaBr | 59 |
6 | Na2SO4 | 36 |
7 | C6H7SO3Na | 66 |
Increase in product yield is due to the hole scavenging effect of the iodide ion. The iodide ion was oxidized to iodine by holes generated by the irradiation of N-TiO2. Consequently the decrease in oxidation by holes will increase the reduction of nitrobenzene (Scheme 1).
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Scheme 1 Mechanism for iodide participating in photocatalytic conversion of nitrobenzene to quinaldine. |
Run | Catalyst | UV light (%) | Visible light (%) |
---|---|---|---|
a All reactions were performed with a 25 mM alcoholic solution of reactant, 50 mg of catalyst, N2 flow rate = 6.1 mL s−1, 300 W Tungsten lamp illumination, irradiation time = 5 h. | |||
1 | Prepared TiO2 | 60 | 16 |
2 | Ag–TiO2 | 65 | 45 |
3 | Au–TiO2 | 75 | 51 |
4 | Pt–TiO2 | 70 | 56 |
5 | N-TiO2 | 70 | 62 |
No product was obtained without the catalyst under visible light (>400 nm) after 5 h, while the yield of quinaldine from nitrobenzene was 16% with bare TiO2 in 5 h. The results reveal that N-TiO2 shows the best catalytic activity among the five catalysts under visible light. Order of activity of the catalysts for the synthesis of quinaldine from nitrobenzene using visible light is N-TiO2 > Pt–TiO2 > Au–TiO2 > Ag–TiO2 > bare TiO2.
All doped catalysts are more efficient than bare TiO2. The highest efficiency of N-TiO2 is due to its increased visible light absorption when compared to other doped catalysts.
Footnote |
† Electronic Supplementary Information (ESI) available: See DOI: 10.1039/c2ra01178f/ |
This journal is © The Royal Society of Chemistry 2012 |