The formation of semiconductor composites comprising multicomponent or multiphase heterojunctions is a very effective strategy to design highly active photocatalyst systems. This review summarizes the recent strategies to develop such composites, and highlights the most recent developments in the fi eld. After a general introduction into the different strategies to improve photocatalytic activity through formation of heterojunctions, the three different types of heterojunctions are introduced in detail, followed by a historical introduction to semiconductor heterojunction systems and a thorough literature overview. Special chapters describe the highly-investigated carbon nitride heterojunctions as well as very recent developments in terms of multiphase heterojunction formation, including the latest insights into the anatase-rutile system. When carefully designed, semiconductor composites comprising two or three different materials or phases very effectively facilitate charge separation and charge carrier transfer, substantially improving photocatalytic and photoelectrochemical effi ciency.

https://faculty.missouri.edu/~glaserr/3700s15/Marschall_Strategies_adfm201303214.pdf

Semiconductor Composites: Strategies for Enhancing Charge Carrier Separation to Improve Photocatalytic Activity

Titanium dioxide (TiO2) has been the most intensively investigated binary transition metal oxide in the past four decades as indicated by Figure S1. Furthermore, the annual number of papers published on TiO2 has seen a continuous increase, particularly since the beginning of this century (Figure S2). This is understandable when one considers the wide range of applications of TiO2 from the conventional areas (i.e., pigment, cosmetic, toothpaste, and paint) to the later developed functional areas such as photoelectrochemical cell,(1-3) dye-sensitized solar cells (DSSCs),(4-11) photocatalysis,(12-24) catalysis,(25-31) photovoltaic cell,(32-34) lithium ion batteries,(35-41) sensors,(42-46) electron field emission,(47-51) microwave absorbing material, biomimetic growth, and biomedical treatments.(52-57) Nearly all these functional applications of TiO2 fall in the scope of energy, environment, and health, which are definitely the three most important and challenging themes facing the Human race that need to be addressed in this century. Besides the apparent merits including nontoxicity, elemental abundance, good chemical stability, and easy synthesis, TiO2 has attracted strong research interest worldwide due to its physicochemical properties for realizing various functions.(15, 58, 59) Especially, very encouraging progresses in photocatalysis and DSSCs with the involvement of TiO2 have greatly stimulated the rapid development of TiO2 crystals with controllable phase, size, shape, defect, and heteroatom.(58, 60-68)

Titanium dioxide crystals with tailored facets

One-dimensional TiO2 nanostructured surface heterostructures (1D TiO2NSHs) have been comprehensively studied during the past two decades because of the possible practical applications in various fields, including photocatalysis, dye-sensitized solar cells, sensors, lithium batteries, biomedicine, catalysis, and supercapacitors. Combining extensive advancements in materials science and nanotechnology, a 1D TiO2NSH material with well-controlled size, morphology, and composition has been designed and synthesized. More importantly, its superior properties, including a high aspect ratio structure, chemical stability, large specific surface area, excellent electronic or ionic charge transfer, and a specific interface effect, have attracted a great deal of interest in improving current performance and exploring new applications. In this tutorial review, we introduce the characteristics of 1D TiO2 nanostructures, the design principles for the fabrication of 1D TiO2NSHs, and we also summarize the recent progress in developing synthesis methods and applications of 1D TiO2NSHs in different fields. The relationship between the secondary phase and the 1D TiO2 nanostructure and between the performance in applications and the excellent physical properties of 1D TiO2NSHs are also discussed.

Recent progress in design, synthesis, and applications of one-dimensional TiO2 nanostructured surface heterostructures: a review

Two-dimensional (2D) nanomaterials are ultrathin nanomaterials with a high degree of anisotropy and chemical functionality. Research on 2D nanomaterials is still in its infancy, with the majority of research focusing on elucidating unique material characteristics and few reports focusing on biomedical applications of 2D nanomaterials. Nevertheless, recent rapid advances in 2D nanomaterials have raised important and exciting questions about their interactions with biological moieties. 2D nanoparticles such as carbon-based 2D materials, silicate clays, transition metal dichalcogenides (TMDs), and transition metal oxides (TMOs) provide enhanced physical, chemical, and biological functionality owing to their uniform shapes, high surface-to-volume ratios, and surface charge. Here, we focus on state-of-the-art biomedical applications of 2D nanomaterials as well as recent developments that are shaping this emerging field. Specifically, we describe the unique characteristics that make 2D nanoparticles so valuable, as well as the biocompatibility framework that has been investigated so far. Finally, to both capture the growing trend of 2D nanomaterials for biomedical applications and to identify promising new research directions, we provide a critical evaluation of potential applications of recently developed 2D nanomaterials.

Two‐Dimensional Nanomaterials for Biomedical Applications: Emerging Trends and Future Prospects

Sol-gel based materials for biomedical applications

As one of the most common chemical materials, titanium dioxide (TiO2) has been prepared and widely used for many years. Among all the applications, the biomedical applications of TiO2 have motivated strong interest and intensive experimental and theoretical studies, owing to its unique photocatalytic properties, excellent biocompatibility, high chemical stability, and low toxicity. Advances in nanoscale science suggest that some of the current problems of life science could be resolved or greatly improved through applying TiO2. This paper presents a critical review of recent advances in the biomedical applications of TiO2, which includes the photodynamic therapy for cancer treatment, drug delivery systems, cell imaging, biosensors for biological assay, and genetic engineering. The characterizations and applications of TiO2 nanoparticles, as well as nanocomposites and nanosystems of TiO2, which have been prepared by different modifications to improve the function of TiO2, are also offered in this review. Additionally, some perspectives on the challenges and new directions for future research in this emerging frontier are discussed.

Recent progress in biomedical applications of titanium dioxide

Solar hydrogen production assisted with semiconductor materials is a promising way to provide alternative energy sources in the future. Such a photocatalytic reaction normally takes place on the active sites of the catalysts surface, and the identification of the active sites is crucial for understanding the photocatalytic reaction mechanism and further improving the photocatalytic efficiency. However, the active sites of model catalysts are still largely disputed because of their structural complexity. Conventionally, H2 evolution from solar water splitting over Pt/TiO2 is widely deemed to take place on metallic Pt nanoparticles. Oppositely, we report through a combined experimental and theoretical approach, that metallic Pt nanoparticles have little contribution to the activity of photocatalytic H2 evolution; the oxidized Pt species embedded on the TiO2 surface are the key active sites and primarily responsible for the activity of the hydrogen evolution Pt/TiO2 photocatalyst.

Active sites on hydrogen evolution photocatalyst

Owing to its scientific and technological importance, crystallization as a ubiquitous phenomenon has been widely studied over centuries. Well-developed single crystals are generally enclosed by regular flat facets spontaneously to form polyhedral morphologies because of the well-known self-confinement principle for crystal growth. However, in nature, complex single crystalline calcitic skeleton of biological organisms generally has a curved external surface formed by specific interactions between organic moieties and biocompatible minerals. Here we show a new class of crystal surface of TiO₂, which is enclosed by quasi continuous high-index microfacets and thus has a unique truncated biconic morphology. Such single crystals may open a new direction for crystal growth study since, in principle, crystal growth rates of all facets between two normal {101} and {011} crystal surfaces are almost identical. In other words, the facet with continuous Miller index can exist because of the continuous curvature on the crystal surface.

/pdf/titania-single-crystals-with-a-curved-surface-3m4pexeda7.pdf

Titania single crystals with a curved surface

Hydrogen-treated commercial WO3 as an efficient electrocatalyst for triiodide reduction in dye-sensitized solar cells

Cuboid-like anatase TiO2 single crystals bounded by {001} and {100} facets have been successfully synthesized with HCl as a synergistic capping agent together with HF, under the guidance of theoretical calculations. DFT calculations suggest that the preferred replacement of HCl with HF at (100) as well as its favorable adsorption provide a unique stabilization effect on the formation of cuboid-like anatase TiO2.

Long Wu

Papers

Recent progress in biomedical applications of titanium dioxide

Active sites on hydrogen evolution photocatalyst

Titania single crystals with a curved surface

Hydrogen-treated commercial WO3 as an efficient electrocatalyst for triiodide reduction in dye-sensitized solar cells

On the synergistic effect of hydrohalic acids in the shape-controlled synthesis of anatase TiO2 single crystals