A surface science perspective on TiO2 photocatalysis

The scientific study of gold nanoparticles (typically 1–100 nm) has spanned more than 150 years since Faraday's time and will apparently last longer. This review will focus on a special type of ultrasmall (<2 nm) yet robust gold nanoparticles that are protected by thiolates, so-called gold thiolate nanoclusters, denoted as Aun(SR)m (where, n and m represent the number of gold atoms and thiolate ligands, respectively). Despite the past fifteen years' intense work on Aun(SR)m nanoclusters, there is still a tremendous amount of science that is not yet understood, which is mainly hampered by the unavailability of atomically precise Aun(SR)m clusters and by their unknown structures. Nonetheless, recent research advances have opened an avenue to achieving the precise control of Aun(SR)m nanoclusters at the ultimate atomic level. The successful structural determination of Au102(SPhCOOH)44 and [Au25(SCH2CH2Ph)18]q (q = −1, 0) by X-ray crystallography has shed some light on the unique atomic packing structure adopted in these gold thiolate nanoclusters, and has also permitted a precise correlation of their structure with properties, including electronic, optical and magnetic properties. Some exciting research is anticipated to take place in the next few years and may stimulate a long-lasting and wider scientific and technological interest in this special type of Au nanoparticles.

Quantum sized, thiolate-protected gold nanoclusters

The electronic excited states of molecular aggregates and their photophysical signatures have long fascinated spectroscopists and theoreticians alike since the advent of Frenkel exciton theory almost 90 years ago. The influence of molecular packing on basic optical probes like absorption and photoluminescence was originally worked out by Kasha for aggregates dominated by Coulombic intermolecular interactions, eventually leading to the classification of J- and H-aggregates. This review outlines advances made in understanding the relationship between aggregate structure and photophysics when vibronic coupling and intermolecular charge transfer are incorporated. An assortment of packing geometries is considered from the humble molecular dimer to more exotic structures including linear and bent aggregates, two-dimensional herringbone and “HJ” aggregates, and chiral aggregates. The interplay between long-range Coulomb coupling and short-range charge-transfer-mediated coupling strongly depends on the aggregate ...

Expanded Theory of H- and J-Molecular Aggregates: The Effects of Vibronic Coupling and Intermolecular Charge Transfer.

Photocatalytic water splitting using particulate semiconductor materials has been studied as a simple means of hydrogen production. However, there are still many obstacles to the development of complete, practical and renewable solar hydrogen production processes. This review discusses particulate photocatalyst systems intended for large-scale solar hydrogen production via water splitting, focusing on their current status and potential impact. The cost and efficiency targets for solar-to-fuel conversion on a practical scale are also reviewed, based on the maximum allowable cost of solar hydrogen production systems, which has been estimated to be US$102 m–2, at most. Particulate photocatalyst material design principles are discussed, using efficient oxide photocatalysts as examples. Approaches to constructing photocatalytic reactors extensible to large areas are also introduced. Finally, challenges related to the development of efficient and inexpensive photocatalyst systems and potentially useful analytical methods are outlined. Photocatalytic water splitting with particulate semiconductors represents a promising strategy for the generation of hydrogen as a solar fuel. This review covers recent advances in the development of reaction systems and photocatalysts towards the scale-up of this technology, emphasizing at the same time the challenges to overcome.

Reaction systems for solar hydrogen production via water splitting with particulate semiconductor photocatalysts

Organic (opto)electronic materials have received considerable attention due to their applications in thin-film-transistors, light-emitting diodes, solar cells, sensors, photorefractive devices, and many others. The technological promises include low cost of these materials and the possibility of their room-temperature deposition from solution on large-area and/or flexible substrates. The article reviews the current understanding of the physical mechanisms that determine the (opto)electronic properties of high-performance organic materials. The focus of the review is on photoinduced processes and on electronic properties important for optoelectronic applications relying on charge carrier photogeneration. Additionally, it highlights the capabilities of various experimental techniques for characterization of these materials, summarizes top-of-the-line device performance, and outlines recent trends in the further development of the field. The properties of materials based both on small molecules and on conjug...

Organic Optoelectronic Materials: Mechanisms and Applications

Photochemical CH bond activation of methane on a Pt(111) surface

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Photochemical CH bond activation of methane on a Pt(111) surface