Gold Modified N-doped TiO 2 and N-doped WO 3 /TiO 2 Semiconductors - Photocatalysts for UV-Visible Light Destruction of 2, 4, 6-Trinitrotoluene in Aqueous

Solution
D. Tomova, V. Iliev, S. Rakovsky, A. Eliyas, M. Anachkov Institute of Catalysis, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria Introduction The subject of the study is the photooxidation removal process of 2, 4, 6trinitrotoluene (TNT), which is one of the most stable and recalcitrant explosives and it does not occur naturally in the environment. TNT is contained in groundwater and soil at numerous industrial sites, which are located in explosive manufacturing plants, packing, storage and military-related facilities. TNT is toxic, mutagenic and a suspected carcinogen, with an EPA lifetime health advisory of 2 g/L. The aim of the study was to obtain nanosized photocatalysts based on oxide semiconducting materials, capable of utilizing the UV-Visible components of the solar light. Experimental N-doped TiO 2 and N-doped WO 3 /TiO 2 nanosized photocatalysts were prepared using the sol-gel method. N-doped TiO 2 was obtained by mixing a solution of titanium(IV) ethoxide in ethyl alcohol with a water solution of urea. The preparation of N-doped WO 3 /TiO 2 was carried out by mixing a solution of titanium(IV) ethoxide in ethyl alcohol and (NH 4 ) 2WO 3 (4% wt.) with a water solution of urea. The obtained products were: TiO 2 , N-doped TiO 2 and N-doped WO 3 /TiO 2 , all calcined for 3 h at 4200. All prepared photocatalyst samples were modified with nanosized gold particles (1% wt) by the photoreduction method. The characterization of the synthesized catalysts was carried out by several physical methods. The average size of the TiO 2 nanoparticles and that of N-doped TiO 2 was 20 nm, while that of WO 3 /TiO 2 and N-doped WO 3 /TiO 2 were 17 nm. The average size of the Au nanoparticles in the modified photocatalysts was 5 nm. The XPS measurements confirmed the incorporation of N-atoms in the crystal lattice of TiO 2 and WO 3 phase. The N atomic concentrations in the crystal lattice of the TiO 2 and WO 3 /TiO 2 were respectively 1.2% and 0.8%. Results and Discussion

The reaction rates of photocatalytic degradation of TNT in the presence of each photocatalyst follow a pseudo-first kinetic order with respect to the pollutant according to the LangmuirHinshelwood model. Dependence of the rate constants (k app ) of photocatalytic TNT degradation in O 2 presence at 293 K is given in Fig. 1.
0,18 0,16 0,14 0,12

kapp (min )

-1

0,1 0,08 0,06 0,04 0,02 0

iO
2)

iO

Ti O

iO

Ti O

3 /T

-T i

3 /T

A u/ N -T i

3 /T

A u/

-(W

A u/ W

Fig.1. Rate constants (k app ) of photocatalytic degradation of TNT in a batch reactor under irradiation by: - UV light; - visible light On the basis of the study of the photocatalysts the following conclusions can be drawn with respect to their efficiency: 1. N-doped TiO 2 , N-doped WO 3 /TiO 2 and Au modified materials are efficient photocatalysts for water purification from TNT able to use successfully the solar light. 2. Under irradiation with UV light, the photonic efficiency of the N-doped TiO 2 and Ndoped WO 3 /TiO 2 is much higher than that in case of irradiation with visible light. The high values of the rate constants of TNT decomposition under irradiation with UV light are the result of the photocatalytic processes occurring simultaneously on TiO 2 , WO 3 and coupled photocatalyst (photon energy E h band-gap energies of the semiconductors). 3. The photocatalytic activities of Au modified TiO 2 , N-doped TiO 2 and N-doped WO 3 /TiO 2 photocatalysts are increased approximately twice under irradiation with UV or visible light. 4. The increased photocatalytic activity of N-(TiO 2 /WO 3 ) under irradiation with UV or visible light is due to the separation of charges in the composite catalyst and the formation of defects in the nitrogen doped oxides. Acknowledgement: Financial support by National Science Fund, Ministry of Education and Sciences of Bulgaria (Project DO 02-252) is gratefully acknowledged.

A u/ N -(W

3 /T

iO

2)