Atomic‐Scale Mapping of Impurities in Partially Reduced Hollow TiO2 Nanowires

The incorporation of impurities during the chemical synthesis of nanomaterials is usually uncontrolled and rarely reported because of the formidable challenge in measuring trace amounts of often light elements with sub‐nanometer spatial resolution. And yet, these foreign elements (introduced by doping, for example) influence functional properties. We demonstrate how the hydrothermal growth and a partial reduction reaction on hollow TiO₂ nanowires leads to the introduction of parts per millions of boron, sodium, and nitrogen. This doping explains the presence of oxygen vacancies and reduced Ti states at the surface, which enhance the functional properties of TiO₂. Our results were obtained on model metal oxide nanomaterials and they shed light on a general process that leads to the uncontrolled incorporation of trace impurities in TiO₂, thereby, having a strong effect on applications in energy‐harvesting.     

Effect of Ag doping concentration on the electronic and optical properties of anatase TiO2: a DFT-based theoretical study

The electronic and optical properties of pure and Ag-doped anatase TiO₂ have been calculated by spin-polarized density functional theory. Ag-doped TiO₂ with different Ag doping concentrations ranging from 2.08 to 8.33 % was investigated, and the electronic and optical properties evaluated. Substitutional Ag doped at Ti sites introduced Ag 4d states just above the valence-band maximum, which may help in shifting visible-light excited electrons to the conduction band. Our results show that increasing the doping concentration will enhance visible-light absorption up to Ag doping concentration of 6.25 %; however, further increase of the doping concentration leads to a decrease in visible-light absorption. These results indicate the possibility of tailoring the band gap and optical absorption of TiO₂ doped with Ag by varying the doping concentration. The enhanced visible-light absorption for Ag-doped TiO₂ with doping concentration of 6.25 % may be due to the existence of widely distributed Ag 4d states above the valence-band maximum and the optimal doping concentration. Ag doping shifted the absorption edge of TiO₂ towards visible light, consistent with recent experimental results. Our calculation results provide a reasonable explanation for the experimental findings.     

Modifications on reduced titanium dioxide photocatalysts: A review

A large variety of reduced titanium dioxide (TiO_2-x) materials have been reported recently. Reduced TiO₂, usually resulting from the removal of oxygen atoms or hydrogen incorporation, is proved to be efficient for achieving highly photocatalytic performance including photodegradation of organic compounds, hydrogen generation from water splitting, CO₂ reduction for CH₄ evolution, solar cells, etc. To further improve the properties and activities of TiO_2-x, a combination of the Ti³⁺ self-doping and other traditional modifications like nonmetals doping has been proposed in the past decades. This paper provides a general and critical review on the further modifications on reduced TiO₂ samples, including non-metal elements (N, B, S, F and I) doping, noble-metal (Au, Pt, Pd and Ag) and iron-group metal (Fe, Co and Ni) grafting, metal oxide compositing, carbon (nanotubes and graphene) and carbon-based-material compositing, special facets exposure (mainly dual {001}-{101} and {111}-{110} facets) of TiO_2-x and ordered structure controlling of TiO_2-x. These modifications enhance the physical and/or chemical properties of the reduced TiO₂, or create new features for the modified TiO_2-x samples, which finally leads to the enhancement of photocatalytic performance. Key examples such as N-doping, Au grafting and graphene-based compositing are discussed carefully, and the mechanisms for solar light enhancement, electron transfer and charge separation are also investigated. Finally, some challenging issues on TiO_2-x catalysts are also proposed to encourage new approaches for preparation of TiO_2-x catalysts with efficiently photocatalytic performance.     

Hydrothermal synthesis of TiO2 nanorods: formation chemistry,growth mechanism,and tailoring of surface properties for photocatalytic activities

Titanium dioxide (TiO₂) is one of the best semiconductor photocatalysts with optical band gap of 3.2 eV. The optical band gap and photocatalytic properties could be further tuned by tailoring shape, size, composition, and morphology of the nanostructures. Hydrothermal synthesis methods have been applied to produce well-controlled nanostructured TiO₂ materials with different morphologies and improved optoelectronic properties. Among various morphologies, one-dimensional (1D) TiO₂ nanostructures are of great importance in the field of energy, environmental, and biomedical because of the directional transmission properties resulting from their 1D geometry. Particularly, TiO₂ nanorods (NRs) have gained special attention because of their densely packed structure, quantum confinement effect, high aspect ratio, and large specific surface area that could specially improve the directional charge transmission efficiency. This results in the effective photogenerated charge separation and light absorption, which are really important for potential applications of TiO₂-based materials for photocatalytic and other important applications. In this review, hydrothermal syntheses of TiO₂ NRs including the formation chemistry and the growth mechanism of NRs under different chemical environments and effects of various synthesis parameters (pH, reaction temperature, reaction time, precursors, solvents etc.) on morphology and optoelectronic properties have been discussed. Recent developments in the hydrothermal synthesis of TiO₂ NRs and tailoring of their surface properties through various modification strategies such as defect creation, doping, sensitization, surface coating, and heterojunction formation with various functional nanomaterials (plasmonic, oxide, quantum dots, graphene-based nanomaterials, etc.) have been reported to improve the photocatalytic activities. Furthermore, applications of TiO₂ NRs/tailored TiO₂ NRs as superior photocatalysts in degradation of organic pollutants and bacterial disinfection have been discussed with emphasis on mechanisms of action and recent advances in the fields.     

Comparison of optical and structural properties of nanostructure TiO2 thin film doped by Sn and Nb

The thin films of TiO₂ doped by Sn or Nb were prepared by sol–gel method under process control. The effects of Sn and Nb doping on the structural, optical and photo-catalytic properties of applied thin films have been studied by X-ray diffraction (XRD) high resolution transmission electron microscopy and UV–Vis absorption spectroscopy. Surface chemical state of thin films was examined by atomic X-ray photoelectron spectroscopy. XRD results suggest that adding impurities has a great effect on the crystallinity and particle size of TiO₂. Titania rutile phase formation in thin film was promoted by Sn⁴⁺ addition but was inhibited by Nb⁵⁺ doping. The activity of the photocatalyst was evaluated by photocatalytic degradation kinetics of aqueous methylene blue under UV and Visible radiation. The results show that the photocatalytic activity of the Sn-doped TiO₂ thin film have a larger degradation efficiency than Nb-doped TiO₂ under visible light, but under UV light photocatalytic activity of the Nb-doped TiO₂ thin film is better.     

Review on Undoped/Doped TiO2 Nanomaterial; Synthesis and Photocatalytic and Antimicrobial Activity

This review covers the various synthetic methods of doped and undoped TiO₂ nanomaterials, ranging from single‐doped and co‐doped to multidoped with transition‐metal ions, rare earth metal ions, and other metals and nonmetals ions. The effects of doping on the physiochemical propertiesas well as the photocatalytic and antimicrobial activities of TiO₂ nanomaterial are discussed. The results from the literature show that doping of TiO₂ shifts the absorption edge to the visible region as a result of the decrease in the bandgap due to the formation of new energy levels in the bandgap. The dopent also acts as a trapping center for electrons and holes, thereby reducing the recombination rate of charge carriers and increasing the photocatalytic and antimicrobial activity of TiO₂ nanomaterials. All multidoped TiO₂ nanomaterials show higher activity than their undoped, single‐doped, and co‐doped counterparts.     

Visible light responsive TiO2 modification with nonmetal elements

Developing visible light responsive (VLR) TiO₂ photocatalysts is essential and attractive for the consideration of solar energy utilization. A large amount of work have shown TiO₂ modified with several nonmetal elements having VLR performance, although according to DFT calculation, Asahi denied the VLR properties of fluorine, carbon, etc. in doping TiO₂. Therefore, the origins of VLR activity desire further delicate discussion. In this mini-review, several strategies for VLR TiO₂ modification have been introduced, including N doping or B/N codoping, surface modification with sensitizing matter such as carbonaceous or other organic substances, surface alkoxyls modification via a ligand-to-metal charge transfer (LMCT) process, and enhanced dye sensitization by fluorine modification. Besides doping, there are much more approaches to fabricate VLR TiO₂ modified with nonmetal elements. However, it is still in demand to explore new methods to obtain more stable and efficient VLR TiO₂ for practical application.     

On the Origin of the Visible‐Light Activity of Titanium Dioxide Doped with Carbonate Species

Plane‐wave‐based pseudopotential density functional theory (DFT) calculations are used to elucidate the origin of the high photocatalytic efficiency of carbonate‐doped TiO₂. Two geometrically possible doping positions are considered, including interstitial and substitutional carbon atoms on Ti sites. From the optical absorption properties calculations, we believe that the formation of carbonates after doping with interstitial carbon atoms is crucial, whereas the contribution from the cationic doping on Ti sites is negligible. The carbonate species doped TiO₂ exhibits excellent absorption in the visible‐light region of 400–800 nm, in good agreement with experimental observations. Electronic structure analysis shows that the carbonate species introduce an impurity state from Ti 3d below the conduction band. Excitations from the impurity state to the conduction band may be responsible for the high visible‐light activity of the carbon doped TiO₂ materials.     

First‐Principles Calculations on Electronic Structures of N/V‐Doped and N‐V‐Dodoped Anatase TiO2 (101) Surfaces

The energetic and electronic properties of N/V‐doped and N‐V‐codoped anatase TiO₂ (101) surfaces are investigated by first‐principles calculations, with the aim to elucidate the relationship between the electronic structure and the photocatalytic performance of N‐V‐codoped TiO₂. Several substitutional and interstitial configurations for the N and/or V impurities in the bulk phase and on the surface are studied, and the relative stability of different doping configurations is compared by the impurity formation energy. Systematic calculations reveal that N and V impurities can be encapsulated by TiO₂ to form stable structures as a result of strong N‐V interactions both in the bulk and the surface model. Through analyzing and comparing the electronic structures of different doping systems, the synergistic doping effects are discussed in detail. Based on these discussions, we suggest that N_OV_Ti codoping cannot only narrow the band gap of anatase TiO₂, but also forms impurity states, which are propitious for the separation of photoexcited electron–hole pairs. In the case of N_OV_Ti‐codoped TiO₂ (101) surfaces, this phenomenon is especially prominent. Finally, a feasible synthesis route for N_OV_Ti codoping into anatase TiO₂ is proposed.     

Enhanced photo-catalytic activity of TiO2 nanostructured thin films under solar light by Sn and Nb co-doping

In this study, preparation of Sn and Nb co-doped TiO₂ dip-coated thin films on glazed porcelain substrates via sol–gel process have been investigated. The effects of co-doping content on the structural, optical, and photo-catalytic properties of applied thin films have been studied by X-ray diffraction (XRD), field emission SEM (FE-SEM), high resolution transmission electron microscopy (HR-TEM), and UV–Vis absorption spectroscopy. Surface chemical state of thin films was examined by atomic X-ray photoelectron spectroscopy (XPS). XRD results suggest that adding impurities has a great effect on the crystallinity and particle size of TiO₂. Titania Rutile phase formation in thin film was promoted by Sn⁴⁺ addition but was inhibited by Nb⁵⁺ doping. The prepared co-doped TiO₂ photo-catalyst films showed optical absorption edge in the visible light area and exhibited excellent photo-catalytic ability for degradation of methylene blue (MB) solution under solar irradiation. Comparison with undoped and Sn or Nb-doped TiO₂, codoped TiO₂ shows an obviously higher catalytic activity under solar irradiation.     

S-, N- and C-doped titanium dioxide nanoparticles: Synthesis, characterization and redox charge transfer study

Herein we report on the synthesis and characterization of TiO₂ nanomaterials doped with anions like sulfur, carbon and nitrogen. Upon doping, the absorption extends well into the visible region. This shift in the absorption edge is accompanied by a concomitant narrowing of band gap. The resulting anion-doped TiO₂ nanomaterials were characterized by XRD, XPS, elemental analysis, EDAX, TEM, UV-DRS, DC conductivity, AC impedance and cyclic voltammetric studies. XPS confirms the presence of the dopants and the elemental analysis determined the amount of dopants in TiO₂. Electrochemical characterization was carried out by cyclic voltammetry at pHs 2, 6.5 and 10. As against the response of undoped TiO₂, the doped samples show an active electrochemical response indicating an induced charge transfer across the titania/solution interface, thus forming two anodic peaks and a cathodic peak. This interesting and significant observation was understood in terms of band bending due to anion doping as well as to the pH changes in the experimental solutions.     

Nano-titanium oxide doped with gold,silver, and palladium — synthesis and structural characterization

Nano-titania doped with noble metals (Au/TiO₂, Ag/TiO₂, Pd/TiO₂) has been synthesized by mild hydrolysis of the mixture of metal salts or complexes and titanium isopropoxide ((iPr-O)₄Ti). After thermal decomposition of the obtained precursors, nanomaterials were formed. Morphological characterization of the nanomaterials was provided by scanning electron microscopy (SEM) and stereological analysis, determining the BET specific surface area, and BJH nanoporosity (pore volume, pore size). It has been found that the structure of nanomaterials (size of nanoparticles and agglomerates) depended strongly on the method of the (iPr-O)₄Ti hydrolysis. A minor dependence on the kind of solvents and precursors of noble metals was observed. The presence of doping metal nanoparticles was confirmed by transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX). Nanomaterial phases were identified by X-ray diffraction (XRD). According to the XRD patterns, Ag/TiO₂ and Pd/TiO₂ products with doping metals in their oxidized form contain Ag-Ti and Pd-Ti phases. Peaks of the metal oxides Ag₂O and PdO are absent in the XRD patterns. The average size of TiO₂ nanoparticles is situated in the region of 20–60 nm, whereas metals are present as about 10–15 nm sized particles and fine nanoparticles.     

High temperature stability and photocatalytic activity of nanocrystalline anatase powders with Zr and Si co-dopants

TiO₂ nanopowders doped by Si and Zr were prepared by sol–gel method. The effects of Si and Zr doping on the structural, optical, and photo-catalytic properties of titania nanopowders have been studied by X-ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy, and UV–Vis absorption spectroscopy. XRD results suggest that adding impurities has a significant effect on anatase phase stability, crystallinity, and particle size of TiO₂. Titania rutile phase formation in ternary system (Ti–Si–Zr) was inhibited by Zr⁴⁺ and Si⁴⁺ co-doped TiO₂ in high temperatures (500–900 °C) and 36 mol% anatase composition is retained even after calcination at 1,000 °C. The photocatalyst activity was evaluated by photocatalytic degradation kinetics of aqueous methylen orange under visible radiation. The results show that the photocatalytic activity of the 20 %Si and 15 %Zr co-doped TiO₂ nanopowders have a larger degradation efficiency than pure TiO₂ under visible light.     

Electronic structure,photocatalytic properties and phonon dispersions of X-doped (X = N,B and Pt) rutile TiO2 from density functional theory

First principles calculations were performed on the electronic, vibrational and Raman spectra of substitutional N-, B- and Pt-doped rutile titanium dioxide (TiO₂), within the density functional theory (DFT), using the plane-wave pseudopotential method. From the calculated electronic band structure and density of states we concluded that the doping induces significant changes in the band structure of TiO₂, highlighting B- and Pt-doped TiO₂ as the best candidates for photocatalytic materials for visible light absorption. On the other hand, N-doped TiO₂ appears to be active only for the photoreduction processes, although N doping introduces midstates into the band gap. Only N-doped TiO₂ proved to have stable phonon dispersions and showed interesting band doubling.     

Surface Modifications and Optoelectronic Characterization of TiO2‐Nanoparticles: Design of New Photo‐Electronic Materials

TiO₂ nanoparticles are of great current interest for applications in photo‐electronic materials including light‐energy conversion, artificial photosynthetic systems as well as photocatalysis. The success of these applications relies on the exciton recombination dynamics and visible‐light sensitivity of the TiO₂ nanomaterials. Thus, in order to develop the highly efficient photo‐electronic materials absorbing visible light, different low dimensional TiO₂ nanostructures such as nanodiscs, nanofibers and nanochains were synthesized, and thereafter their surfaces were modified by incorporating with Sn‐porphyrins and heteropoly acid. The optoelectronic properties of the surface‐modified nanomaterials were investigated with regard to the optical properties and the surface exciton dynamics by using both steady‐state and ultrafast time‐resolved laser spectroscopic techniques including single nanoparticle photoluminescence technique. These results were correlated with the photo‐electronic properties including photocatalytic activities and solar cell efficiencies, indicating that the electron transfer mechanism in the modified nanostructures may be similar to the “Z‐scheme” of the plant photosynthetic system so that both photocatalytic activity and solar cell efficiencies were synergistically enhanced by using two color illumination.     

First-Principles Study of La Doping Effects on the Electronic Structures and Photocatalytic Properties of Anatase TiO2

The effects of doping concentration, position and oxygen vacancy defect on the stability, electronic and optical properties of La-doped anatase TiO₂ have been investigated based on DFT+U method. The calculations indicated that the doping concentration and sites of La affected the stability and band gap of La-doped TiO₂ significantly due to the lattice distortion, which obey the ionic Pauling’s rules and crystal field theories; moreover, the simulated adsorption spectrum shows an obviously increase in the photocatalysis properties, which are in good agreement with recently experimental measurements. The oxygen vacancy defect will enhance the structural stability and the adsorption of visible light in La-doped TiO₂ system, which is important in photocatalytic application.     

Photocatalytic Degradation of Glyphosate in Water by N‐Doped SnO2/TiO2 Thin‐Film‐Coated Glass Fibers

Photocatalytic degradation of glyphosate contaminated in water was investigated. The N‐doped SnO₂/TiO₂ films were prepared via sol–gel method, and coated on glass fibers by dipping method. The effects of nitrogen doping on coating morphology, physical properties and glyphosate degradation rates were experimentally determined. Main variable was the concentration of nitrogen doping in range 0–40 mol%. Nitrogen doping results in shifting the absorption wavelengths and narrowing the band gap energy those lead to enhancement of photocatalytic performance. The near optimal 20N/SnO₂/TiO₂ composite thin film exhibited about two‐ and four‐folds of glyphosate degradation rates compared to the undoped SnO₂/TiO₂ and TiO₂ films when photocatalytic treatment were performed under UV and solar irradiations, respectively, due to its narrowest band gap energy (optical absorption wavelength shifting to visible light region) and smallest crystallite size influenced by N‐doping.     

氮掺杂二氧化钛粉体的制备及掺杂机理研究

以钛酸四丁酯为钛源,尿素为氮源制备了N掺杂二氧化钛粉体。采用X射线衍射、透射电镜和紫外-可见吸收光谱对粉体晶粒尺寸、物相及光吸收性质进行了表征。结果表明,N掺杂有效抑制了二氧化钛晶粒的长大,并使TiO₂光吸收效果大大提高。采用密度泛函方法对掺杂机理进行研究证明,N掺杂有效减小了TiO₂带隙宽度,使吸收谱红移,相比替位氮掺杂,间隙氮掺杂更有利于提高光吸收效率。     

掺杂Fe2O3对吸附相反应技术制备TiO2的形貌和光催化性能的影响

利用吸附相反应技术制备得到了掺杂不同浓度的Fe₂O₃的TiO₂复合光催化剂。通过透射电子显微镜(TEM)、紫外可见光谱和X射线衍射(XRD)研究不同掺杂浓度对TiO₂形貌和结晶过程的影响,并利用3种波长光源下的甲基橙光降解实验考评了各个复合光催化剂的催化活性。结果表明,掺杂后复合光催化剂中Fe₂O₃分散性较好较均匀。在TiO₂紫外可见吸收光谱中由于Fe₂O₃的掺杂而出现了红移,而且随着掺杂浓度增加红移越来越明显,复合光催化剂的禁带宽度也越来越小。在焙烧过程中无定形Fe₂O₃或Fe³⁺进入了TiO₂的晶格结构,从而抑制了TiO₂的结晶过程。半导体禁带宽度的减少以及TiO₂结晶过程的抑制作用,都导致紫外光下复合光催化剂催化活性的降低。但Fe₂O₃的掺杂也使得复合光催化剂在可见光区出现了一定的光催化活性。     

氮掺杂二氧化钛粉体的制备及掺杂机理研究

以钛酸四丁酯为钛源,尿素为氮源制备了N掺杂二氧化钛粉体。采用X射线衍射、透射电镜和紫外-可见吸收光谱对粉体晶粒尺寸、物相及光吸收性质进行了表征。结果表明,N掺杂有效抑制了二氧化钛晶粒的长大,并使TiO2光吸收效果大大提高。采用密度泛函方法对掺杂机理进行研究证明,N掺杂有效减小了TiO2带隙宽度,使吸收谱红移,相比替位氮掺杂,间隙氮掺杂更有利于提高光吸收效率。