Novel continuous single-step synthesis of nitrogen-modified TiO2 by flame spray pyrolysis for photocatalytic degradation of phenol in visible light

doi:10.1016/j.jmst.2018.04.014

Abstract

Abstract:

A novel rapid and continuous process has developed for the synthesis of nitrogen-doped TiO₂ (N-TiO₂) with flame spray pyrolysis (FSP) method. The nitrogen incorporation into TiO₂ was achieved by a facile modification (addition of dilute nitric acid) in the precursor for the synthesis. The catalysts were characterized by X-ray diffraction, Raman spectroscopy, transmission electron microscopy, diffuse reflectance spectroscopy, and X-ray photoelectron spectroscopy. The doping of nitrogen into the TiO₂ was confirmed by X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray (EDX) spectroscopy. The UV-vis spectra of the modified catalysts (with primary N source) exhibited band-gap narrowing for 4N-TiO₂ with band gap energy of 2.89 eV, which may be due to the presence of nitrogen in TiO₂ structure. The introduction of secondary N-source (urea) into TiO₂ crystal lattice results in additional reduction of the band gap energy to 2.68 eV and shows a significant improvement of visible light absorption. The N-TiO₂ nanoparticles modified by using secondary N-source showed significant photocatalytic activity under visible light much higher than TiO₂. The higher activity is attributed to the synergetic interaction of nitrogen with the TiO₂ lattice. The lowering of the band-gap energy for the flame made N-doped TiO₂ materials implies that the nitrogen doping in TiO₂ by aerosol method is highly effective in extending the optical response of TiO₂ in the visible region. The nitrogen atomic percentage has increased monotonically (0.09%-0.15%) with the increase in primary nitrogen source (nitric acid), and significantly boosted to 0.97% when secondary nitrogen source (urea) was introduced. The highest rate of phenol degradation was obtained for catalysts with secondary N source due to increase in N content in the catalyst.

Key words: Flame spray pyrolysis (FSP), Titania, (TiO₂), Visible-light-induced, Liquid phase, Phenol photodegradation

Thirupathi Boningari, Siva Nagi Reddy Inturi, Makram Suidan, Panagiotis G.Smirniotis. Novel continuous single-step synthesis of nitrogen-modified TiO₂ by flame spray pyrolysis for photocatalytic degradation of phenol in visible light[J]. J. Mater. Sci. Technol., 2018, 34(9): 1494-1502.

Figures/Tables 10

Fig. 1. (a) Powder X-ray diffraction patterns of all the as-synthesized samples, (b) magnified view of the diffraction peak shift, and (c) effect of secondary N-source (urea).

Table 1 XRD and BET characterization results for FSP TiO2 and N-doped TiO2 samples.

Catalyst	Surface area analysis				X-ray diffraction analysis
	SSA (m²/g)	d_BET^b(nm)	Pore volume (cm³/g)	Pore Diameter (nm)	X_Anatase^c (%)	d_A^d(nm)	d_R^d(nm)	d_xrd^e(nm)
FSP TiO₂	98.6	15	0.287	11.7	81	16.1	24.4	17.7
0.8N-TiO₂	22.1	67	0.079	13.6	56	70.9	59.3	65.9
1N-TiO₂	24.4	61	0.086	12.9	62	59.1	89.0	70.4
1.5N-TiO₂	28.2	53	0.082	11.4	61	50.6	44.5	48.3
2N-TiO₂	27.3	55	0.101	14.7	62	59.1	59.3	59.2
2.5N-TiO₂	25.4	59	0.088	13.6	55	32.2	35.6	33.7
3N-TiO₂	23.7	63	0.063	10.3	56	40.5	37.0	39.0
4N-TiO₂	22.4	67	0.088	14.2	62	44.3	71.2	54.3
1-1N-TiO₂	22.1	68	0.083	20.8	59	70.9	70.9	70.9

Fig. 2. Raman spectra of all the prepared samples: (a) effect of primary N-source, (b) effect of secondary N-source (urea).

Fig. 3. N2 adsorption/desorption isotherms of selected as-synthesized catalysts.

Fig. 4. UV-vis diffuse reflectance spectra of (a) FSP TiO2, 0.8N-TiO2, 1N-TiO2, 2N-TiO2, 3N-TiO2, and 4N-TiO2, (b) FSP TiO2, 0.8N-TiO2, 4N-TiO2 and 1-1N-TiO2.

Table 2 UV-vis characterization and nitrogen atomic percentage from XPS analysis.

Catalyst	Uv-vis region	Band gap (eV)	N (Atomic) %^a
FSP TiO₂	UV	3.11	-
0.8N-TiO₂	Visible	2.96	0.09
1N-TiO₂	Visible	2.95	0.11
1.5N-TiO₂	Visible	2.94	0.11
2N-TiO₂	Visible	2.91	0.15
2.5N-TiO₂	Visible	2.90	0.15
3N-TiO₂	Visible	2.89	0.13
4N-TiO₂	Visible	2.89	0.12
1-1N-TiO₂	Visible	2.68	0.97

Fig. 5. TEM and SAED patterns of as-prepared flame-made catalysts (a) FSP TiO2, (b) 0.8N-TiO2, (c) 4N-TiO2 and (d) 1-1N-TiO2.

Fig. 6. (a) X-ray photoelectron survey spectra, (b) and (c) effect of primary and secondary N-sources on deconvoluted N 1 s spectra, respectively.

Table 3 Elemental analysis of the as-synthesized TiO2 and N-doped TiO2 samples by EDX and XPS.

Catalyst	Atomic percentage from XPS	Atomic percentage from EDX
	Atomic percentage from XPS	N	O	Ti
FSP TiO₂	0.0	0.0	69.10	30.90
1.5N-TiO₂	0.11	0.08	55.82	44.11
2.5N-TiO₂	0.15	0.74	64.58	34.68
3.0N-TiO₂	0.13	0.17	59.66	40.16
1-1N-TiO₂	0.97	1.32	59.02	39.66

Fig. 7. Visible photo degradation of aqueous phenol with respect to time (a) effect of nitric acid as a primary source, (b) effect of urea as a secondary source; catalyst concentration 0.5 g/L, T = 25 °C, initial concentration of phenol = 500 ppm.

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Novel continuous single-step synthesis of nitrogen-modified TiO₂ by flame spray pyrolysis for photocatalytic degradation of phenol in visible light

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