Titanium Dioxide Nanomaterials: Synthesis, Properties, Modifications, and Applications

A surface science perspective on TiO2 photocatalysis

Photocatalysts and Photoelectrodes James L. White,† Maor F. Baruch,† James E. Pander III,† Yuan Hu,† Ivy C. Fortmeyer,† James Eujin Park,† Tao Zhang,† Kuo Liao,† Jing Gu,‡ Yong Yan,‡ Travis W. Shaw,† Esta Abelev,† and Andrew B. Bocarsly*,† †Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States ‡Chemical and Materials Science Center, National Renewable Energy Laboratory, Golden, Colorado 80401, United States

Light-Driven Heterogeneous Reduction of Carbon Dioxide: Photocatalysts and Photoelectrodes

Nitrogen-doped TiO2 nanocatalysts with a homogeneous anatase structure were successfully synthesized through a microemulsion−hydrothermal method by using some organic compounds such as triethylamine, urea, thiourea, and hydrazine hydrate. Analysis by Raman and X-ray photoemission spectroscopy indicated that nitrogen was doped effectively and most nitrogen dopants might be present in the chemical environment of Ti−O−N and O−Ti−N. A shift of the absorption edge to a lower energy and a stronger absorption in the visible light region were observed. The results of photodegradation or the organic pollutant rhodamine B in the visible light irradiation (λ > 420 nm) suggested that the TiO2 photocatalysts after nitrogen doping were greatly improved compared with the undoped TiO2 photocatalysts and Degussa P-25; especially the nitrogen-doped TiO2 using triathylamine as the nitrogen source showed the highest photocatalytic activity, which also showed a higher efficiency for photodecomposition of 2,4-dichlorophenol. T...

Synthesis and Characterization of Nitrogen-Doped TiO2 Nanophotocatalyst with High Visible Light Activity

Nitrogen doped titanium dioxide is attracting a continuously increasing attention because of its potential as material for environmental photocatalysis In this paper we review experimental and theoretical work done on this system in our groups in recent years The analysis is largely based on electron paramagnetic resonance (EPR) spectra and on their interpretation based on high-level ab initio calculations N-doped anatase TiO2 contains thermally stable single N-atom impurities either as charged diamagnetic Nb- centers or as neutral paramagnetic Nb centers (b stays for bulk) The N-atoms can occupy both interstitial or substitutional positions in the solid, with some evidence for a preference for interstitial sites All types of Nb centers give rise to localized states in the band-gap of the oxide, thus accounting for the related reduction of absorption band edge The relative abundance of these species depends on the oxidation state of the solid In fact, upon reduction, oxygen vacancies form and transfer electrons from Ti3+ ions to the Nb with formation of Ti4+ and Nb- EPR spectra measured under irradiation show that the Nb centers are responsible for visible light absorption with promotion of electrons from the localized N-impurity states to the conduction band or to electron scavengers like O2 adsorbed on the surface These results provide an unambiguous characterization of the electronic states associated with N-impurities in TiO2 and a realistic picture of the processes occurring in the solid under irradiation with visible light

N-doped TiO2: Theory and experiment

Nitrogen-doped TiO2 (N−TiO2) nanocatalyst with spherical shape and homogeneous size has been synthesized through a chemical method using TiCl3 as precursor. The light absorption onset shifts from 380 nm on pure TiO2 to the visible region at 550 nm with N−TiO2. A clear decrease in the band gap and the nitrogen 2p states on the top of the valence band on N−TiO2 (compared to TiO2) is deduced from the optical absorption spectroscopy results. The chemical nature of N has been evolved as N−Ti−O in the anatase TiO2 lattice as identified by X-ray photoelectron spectroscopy (XPS). Photocatalytic decomposition of methylene blue has been carried out both in the UV and in the visible region and N−TiO2 shows higher activity than the Degussa P25 TiO2 photocatalyst in the visible region.

Synthesis, Characterization, Electronic Structure, and Photocatalytic Activity of Nitrogen-Doped TiO2 Nanocatalyst

N,S-co-doped anatase-phase TiO2 (N,S-TiO2) nanophotocatalysts were prepared from either benzothiazoline or aminothiol with titanium isopropoxide followed by a systematic thermal decomposition. The chemical nature of S and N in N,S-TiO2 have been identified by XPS to be sulfate and NO-like, respectively. A significant band broadening and red-shift in the UV-visible absorption spectrum of N,S-TiO2 suggests a band gap reduction compared to TiO2. A maximum band-gap narrowing of 0.22 +/- 0.02 eV was observed on N,S-TiO2. Higher energy width observed on N,S-TiO, is in contrast to 0.13 eV from N-doped TiO2 indicating the sulfate-like species might play a major role in narrowing the band-gap to a higher level. It is confirmed that the oxidation of N and S to NO and SO4(2-) occurs in the final stage of preparation of N,S-TiO2, during calcination in air. It is predicted that the oxygen associated with sulfate and NO structural features could be crucial in bringing down the energy gap and red shift in optical absorption and the role of sulfur is to facilitate the above. Photocatalytic decomposition of methylene blue has been carried out on N,S-TiO2 shows higher activity than the commercial TiO2 in the visible region. However, sulfate species seems to enhance the activity of N,S-TiO2 marginally compared to N-TiO2, and possible suggestions are given to improve the same.

R. P. Viswanath

Papers

Synthesis, Characterization, Electronic Structure, and Photocatalytic Activity of Nitrogen-Doped TiO2 Nanocatalyst

N,S-co-doped TiO2 nanophotocatalyst: synthesis, electronic structure and photocatalysis.