Synthesis and Characterization of Metal Doped Titanium Dioxide, Transition Metal Phosphides, Sulfides and Thiophosphates for Photocatalysis and Energy Applications


Book Description

This thesis covers synthetic investigations, characterization, and applications of transition metal doped titanium dioxide materials and transition metal phosphide/sulfide structures. Both areas are useful in heterogeneous catalysis, battery energy storage, and in semiconductor light to energy conversion. Two main synthesis routes have been investigated: 1) rapid solid state metathesis (SSM) of transition metal oxides, phosphides, sulfides, and thiophosphates, and 2) sealed ampoule routes of transition metal phosphides and thiophosphates. SSM reactions tend to yield kinetically controlled multiphase products while sealed ampoule routes gave more thermodynamically favorable single phase materials. Approximately 10 mol% of many first row transition metals (M = Cr, Mn, Fe, Co, Ni, Cu) were targeted for doping into TiO2, using MClx, and sodium peroxide in SSM reactions, targeting an ideal mixed phase of M0.1Ti0.9O2. X-ray diffraction showed rutile TiO2 forms and no separate dopant metal phases were seen until subsequent 1000 °C annealing in air. EDS, ICP, and XPS analysis showed slightly lower than the targeted M:Ti ratios however, the manganese sample had more than the ideal 10 mol % of dopant. DRS data showed estimated bandgap energies of the doped samples within 1.33-2.55 eV. Magnetic susceptibility showed small paramagnetic responses from all samples that increase upon annealing. SEM showed that the doped SSM-TiO2 samples were mixtures of aggregates and blocky particles. The synthesized doped titanias were tested for methylene blue and methyl orange photodegradation under UV and visible light and for H2 generation from water reduction under UV light. The doped titania samples absorb significant amounts of methylene blue dye in the dark with the manganese doped TiO2 sample being the most absorbent. Degradation of methylene blue under UV illumination was observed, however, only modest degradation under visible light was observed.




Titanium Dioxide


Book Description

Titanium dioxide is mainly used as a pigment and photocatalyst. It is possible to find it in food, cosmetics, building materials, electric devices, and others. This book contains chapters about characteristics of anatase and rutile crystallographic structure of titanium dioxide and the use of theoretical calculation for photoactivity determination.




Titanium Dioxide Photocatalysis


Book Description

Although the seminal work of Fujishima et al. dates back to 1971, TiO2 still remains the most diffused and studied semiconductor, employed in photo-oxidation processes for cleantech (i.e., polluted water and air treatment), in solar fuel production (mainly hydrogen production by water photo splitting), and in Carbon Capture and Utilization (CCU) processes by CO2 photoreduction. The eleven articles, among them three reviews, in this book cover recent results and research trends of various aspects of titanium dioxide photocatalysis, with the chief aim of improving the final efficiency of TiO2-based materials. Strategies include doping, metal co-catalyst deposition, and the realization of composites with plasmonic materials, other semiconductors, and graphene. Photocatalysts with high efficiency and selectivity can be also obtained by controlling the precise crystal shape (and homogeneous size) and the organization in superstructures from ultrathin films to hierarchical nanostructures. Finally, the theoretical modeling of TiO2 nanoparticles is discussed and highlighted. The range of topics addressed in this book will stimulate the reader’s interest as well as provide a valuable source of information for researchers in academia and industry.




Synthesis and Characterization of Nitrogen-doped Titanium Oxide Nanoparticles for Visible-light Photocatalytic Wastewater Treatment


Book Description

TiO2 nanoparticles are one of the most suitable materials for photocatalysis, specifically for water and air treatment and removal of a wide variety of organic pollutants such as dyes, aromatic compounds, and chlorinated aromatic compounds. Methods of synthesis of TiO2 are generally categorized in two main classes of wet chemical, and dry methods. Wet chemical methods generally provide a better control over size, size distribution, and shape; all of which significantly affect photocatalytic performance of the produced nanoparticles. Despite its advantages over other semiconductor photocatalysts, wide band-gap of titania restrains its photocatalytic activity to only UV light, which only makes up to 5% of the light reaching surface of the earth. To induce visible-light activity, titania has been doped by different dopants, including transition metal-dopants such as Fe, and Co and non-metal dopants such as N, and C. Nitrogen has been shown to be a better dopant, providing a suitably placed energy state within the band-gap of TiO2, and not suffering from issues related to transition-metal dopants such as low thermal and physical stability and high electron-hole recombination rates. To dope titania with nitrogen, one could add the nitrogen source together with other precursors during synthesis, referred to as wet chemical doping methods, or anneal the synthesized titania nanoparticles under a flow of ammonia at high temperatures, referred to as dry doping methods. While different doping methods have been studied individually, the author maintains that there has been an absence of research comparing the effectiveness of these methods, on photocatalytic performance of N-doped TiO2 within a consistent experiment. In this research TiO2 nanoparticles were synthesized by a facile, inexpensive sol-gel method, and doping was done by wet chemical methods, dry methods, and a combination of both these methods. Visible-light photocatalytic activity of these nanoparticles was evaluated by their efficiency in degradation of methyl orange. The results show wet doping methods increase the efficiency of titania nanoparticles more than dry doping, or combination of both. Further investigation showed that the main reason for higher activity of wet chemically doped nanoparticles is due to their higher available surface area of 131.7 m2.g-1. After normalizing the available surface area, measured by the BET method, it was shown that a combination of wet chemical doping, and dry doping at 600 °C result in the most active nanoparticles, but high temperature dry doping severely decreases the surface area, lowering the overall efficiency of the product. Additionally, N-doped TiO2 nanoparticles were synthesized using a simple hydrothermal method, in which the nitrogen source was used not only to dope, but also to control shape, size, size distribution, and morphology of the titania nanoparticles, and to induce aqueous colloidal stability. It was shown that addition of triethylamine during the synthesis, results in ultra-small, colloidally stable, cubic TiO2 nanoparticles, while using triethanolamine results in formation of TiO2 pallets, assembled into spherical, rose-like structures. The synthesized nanoparticles show impressive efficiency in visible-light removal of phenol, 4-chlorophenol, and pentachlorophenol, achieving 100% degradation of a 100-ppm phenol solution in 90 min, more than 98% degradation of a 20-ppm 4-chlorophenol solution in 90 min, and 97% degradation of a 10-ppm pentachlorophenol in 180 min with 500 ppm loading of the catalyst in all cases. Moreover, synthesized nanoparticles showed no sign of deactivation after 5 consecutive runs, removing 4-chlorophenol, showing their reusability.




Nanostructured Titanium Dioxide in Photocatalysis


Book Description

Titanium dioxide (TiO2) has drawn considerable attention as an attractive inorganic raw material for various applications due to its inexpensiveness, nontoxic nature, stability, and excellent photocatalytic activity. Photocatalysis is one of the most promising route for sustainable chemistry of the 21st century. It can contribute to solving environmental, global energy, and chemical problems, as well as to the sustainable production of commodities in the near future. This book presents the fundamentals of photocatalysis in nanostructured TiO2 and describes the factors affecting the photocatalytic activity, design, and synthesis of various forms of nanostructured TiO2. It highlights the use of ion-doping and inert-atmosphere annealing to extend the light-absorption range of photocatalysts and reduce recombination between electrons and holes. It discusses numerous applications in the fields of energy and environment, such as water purification, gas sensing, storage and delivery, and energy generation. The book is an invaluable resource and useful guide for a broad readership in various fields of catalysis, materials science, environment, and energy.




Preparation and Characterization of Copper-doped and Silver-doped Titanium Dioxide Nano-catalysts for Photocatalytic Applications


Book Description

The goal of this work was to improve the performance of TiO2 nanomaterials by increasing their optical activities by shifting the onset of the response from the UV to the visible-light region. Among the several ways to achieve this goal, doping TiO2 nanomaterials with other elements (e.g. metals) was selected to narrow the band gap and enhance the optical properties of TiO2 nanomaterials. In this work, we have prepared Cu-doped TiO2 and Ag-doped TiO2 nano-catalysts, characterized them and studied their properties, and the optical ones in particular. The Ag-doped TiO2 catalyst was prepared by the sol-gel method while the Cu-doped TiO2 catalyst was prepared by using two different techniques for comparison purposes: the sol-gel method and the inert gas condensation technique under ultra-high vacuum. The Ag-doped TiO2 nano-catalysts prepared by the sol-gel method were characterized by using Fourier transform infrared spectroscopy (FTIR), Field emission scanning electron microscopy (FESEM) and Electron Probe Micro-Analyser (EPMA) for surface morphology and chemical composition, Brunauer-Emmett-Teller (BET) analysis for surface area and porosity measurements, X-ray diffraction (XRD) to determine their crystal structure and UV-visible absorption spectrometry (UV-Vis) to measure the optical properties. The same characterization methods have been applied on the Cudoped TiO2 photocatalysts prepared by the sol-gel method, in addition to some rheological measurements to determine their flow behaviour. Furthermore, X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and UV-visible absorption spectrometry (UV-Vis) analyses have been conducted to characterize the Cu-doped TiO2 catalysts prepared by the inert gas condensation technique. vii The experimental work conducted here revealed promising results for improving the performance of the TiO2 nano material by doping it with Cu and Ag metals where the optical activity was enhanced and shifted to the visible region causing an appreciable increase in its effectiveness for photo catalytic applications.




Nanostructured Titanium Dioxide Materials


Book Description

During the past decade, research and development in the area of synthesis and applications of different nanostructured titanium dioxide have become tremendous. This book briefly describes properties, production, modification and applications of nanostructured titanium dioxide focusing in particular on photocatalytic activity. The physicochemical properties of nanostructured titanium dioxide are highlighted and the links between properties and applications are emphasized. The preparation of TiO2 nanomaterials, including nanoparticles, nanorods, nanowires, nanosheets, nanofibers, and nanotubes are primarily categorized by their preparation method (sol-gel and hydrothermal processes). Examples of early applications of nanostructured titanium dioxide in dye-sensitized solar cells, hydrogen production and storage, sensors, rechargeable batteries, electrocatalysis, self-cleaning and antibacterial surfaces and photocatalytic cancer treatment are reviewed. The review of modifications of TiO2 nanomaterials is mainly focused on the research related to the modifications of the optical properties of TiO2 nanomaterials, since many applications of TiO2 nanomaterials are closely related to their optical properties. Photocatalytic removal of various pollutants using pure TiO2 nanomaterials, TiO2-based nanoclays and non-metal doped nanostructured TiO2 are also discussed.




Solid State Chemistry and Photocatalysis of Titanium Dioxide


Book Description

Volume is indexed by Thomson Reuters BCI (WoS). The goal of this special volume was to provide a unique opportunity to exchange information, to present the latest results and to review relevant issues affecting contemporary diffusion research. The large number (over 232) of peer-reviewed papers emphasizes the considerable academic and industrial interest in this field.




Titanium Dioxide


Book Description

This book presents a comprehensive overview of titanium dioxide, including recent advances and applications. It focuses on the compound’s uses in environmental remediation, photocatalytic materials, rechargeable lithium-ion batteries, thin films, energy storage, semiconductors, and much more. This volume is a useful resource for researchers, scientists, engineers, and students.




Titanium Dioxide (TiO2) and its Applications


Book Description

Titanium Dioxide (TiO2) and its Applications introduces the main physico-chemical properties of TiO2 that form the basis of its applications in various fields. The book focuses on TiO2 applications, with contributions from experts from a wide range of disciplines who address titanium dioxide's utilization in energy, consumer, materials and devices, and catalytic applications. Applications addressed include photocatalysis, catalysis, optics, electronics, energy storage and production, ceramics, pigments, cosmetics, sensors, heat transfer, and more. This book is ideal for a wide readership in the disciplines of materials science, chemistry and engineering in academia and industry. Includes a wide range of applications of titanium dioxide, both current and emerging, in the fields of energy, consumer applications, materials and devices Provides a brief overview of titanium dioxide and its properties and techniques to design, deposit and study the material Discusses relevant properties, preparation methods, and other considerations in each applications-focused chapter