The interest in nanoscale materials stems from the fact that new properties are acquired at this length scale and, equally important, that these properties * To whom correspondence should be addressed. Phone, 404-8940292; fax, 404-894-0294; e-mail, mostafa.el-sayed@ chemistry.gatech.edu. † Case Western Reserve UniversitysMillis 2258. ‡ Phone, 216-368-5918; fax, 216-368-3006; e-mail, burda@case.edu. § Georgia Institute of Technology. 1025 Chem. Rev. 2005, 105, 1025−1102

Chemistry and properties of nanocrystals of different shapes.

2.3. Evaluation of Photocatalytic Water Splitting 6507 2.3.1. Photocatalytic Activity 6507 2.3.2. Photocatalytic Stability 6507 3. UV-Active Photocatalysts for Water Splitting 6507 3.1. d0 Metal Oxide Photocatalyts 6507 3.1.1. Ti-, Zr-Based Oxides 6507 3.1.2. Nb-, Ta-Based Oxides 6514 3.1.3. W-, Mo-Based Oxides 6517 3.1.4. Other d0 Metal Oxides 6518 3.2. d10 Metal Oxide Photocatalyts 6518 3.3. f0 Metal Oxide Photocatalysts 6518 3.4. Nonoxide Photocatalysts 6518 4. Approaches to Modifying the Electronic Band Structure for Visible-Light Harvesting 6519

Semiconductor-based Photocatalytic Hydrogen Generation

The interest in heterogeneous photocatalysis is intense and increasing, as shown by the number of publications on this theme which regularly appear in this journal, and the fact that over 2000 papers have been published on this topic since 1981. This article is an overview of the field of semiconductor photocatalysis : a brief examination of its roots, achievements and possible future. The semiconductor titanium dioxide (TiO 2 ) features predominantly in past and present work on semiconductor photocatalysis; as a result, in the most of the examples selected in this overview to illustrate various points the semiconductor is TiO 2 .

An overview of semiconductor photocatalysis

Core/Shell Nanoparticles: Classes, Properties, Synthesis Mechanisms, Characterization, and Applications

6. Rehybridization of the Acceptor (RICT) 3908 7. Planarization of the Molecule (PICT) 3909 III. Fluorescence Spectroscopy 3909 A. Solvent Effects and the Model Compounds 3909 1. Solvent Effects on the Spectra 3909 2. Steric Effects and Model Compounds 3911 3. Bandwidths 3913 4. Isoemissive Points 3914 B. Dipole Moments 3915 C. Radiative Rates and Transition Moments 3916 1. Quantum Yields and Radiationless Deactivation Processes 3916

Structural Changes Accompanying Intramolecular Electron Transfer: Focus on Twisted Intramolecular Charge-Transfer States and Structures

The mechanistic and kinetic details of the charge injection from excited CdS into a large bandgap semiconductor such as AgI and TiO{sub 2} have been investigated by coupling the two semiconductor systems in the colloidal form. The interaction between the two colloids led to the quenching of CdS emission. The rate constants for the charge injection from excited CdS into the conduction band of AgI and TiO{sub 2} colloids were determined to be 2.2 {times} 10{sup 7} and >5 {times} 10{sup 10} s{sup {minus}1}, respectively. Transmission electron microscopic analysis indicated the possibility of several CdS colloidal particles interacting with a single particle of TiO{sub 2} and participating in the charge injection process. Primary photochemical events in the CdS-TiO{sub 2} system were investigated by picosecond laser flash photolysis. The charge injected into the TiO{sub 2} colloid and trapped at the Ti{sup 4+} site was characterized from its broad absorption in the region of 500-760 nm. The extended lifetime of these trapped charge carriers indicated an improved charge separation in the coupled semiconductor system.

Photophysical and photochemical aspects of coupled semiconductors: charge-transfer processes in colloidal cadmium sulfide-titania and cadmium sulfide-silver(I) iodide systems

A palladium-nanoparticle-cored G-3 dendrimer, characterized by TEM, TGA, absorption, and IR spectroscopies, has approximately 300 Pd atoms in the metallic core and an average diameter of 2.0 nm, to which are attached fourteen G-3 dendrons. Nearly 90% of the metal nanoparticle surface is unpassivated and available for catalysis. The dendrons inhibit metal agglomeration without adversely affecting chemical reactivity. Thus, preliminary investigations have shown that Pd-G-3 can efficiently catalyze Heck and Suzuki reactions.

Synthesis, Characterization, and Catalytic Applications of a Palladium-Nanoparticle-Cored Dendrimer

Photophysical investigation of similarities between starburst dendrimers and anionic micelles

The synthesis and characterization of a group of new dendrimersnamely, nanoparticle-cored dendrimers (NCDs)are described. These materials were obtained by the reduction of hydrogen tetrachloroaurate phase-transferred into toluene in the presence of Frechet-type polyaryl ether dendritic disulfide wedges of generation 1−5. These materials, possessing nanometer-sized gold clusters at the core and dendritic wedges radially connected to the core by Au−S bonds, were analyzed by TEM and TGA, and by UV, IR, and NMR spectroscopies. The number of branching units connected to the core decreased with the generation of the dendritic wedge, and this number changed from 2.18/nm2 for Au−G-2 to 0.27/nm2 for Au−G-5. This result suggests that, in the higher-generation NCDs, a large fraction of the surface area of the metal cluster is not passivated and is therefore available for catalytic activity.

Nanoparticle-cored dendrimers: synthesis and characterization.

Triphenylamine (TPA) derivatives react with Cu2+ in acetonitrile to give TPA radical cations which undergo dimerization and deprotonation reactions to yield tetraphenylbenzidines (TPB). Synthetic utility of this reaction is demonstrated using several triphenylamine derivatives, and yields in excess of 80% are obtained in most cases. Involvement of the amine radical cations in these reactions was confirmed by ESR and absorption spectroscopic studies. A mechanism consistent with all observations is proposed. This study also revealed a very good correlation between the free energy change for radical cation formation and product yields.

Karical R. Gopidas

Papers

Photophysical and photochemical aspects of coupled semiconductors: charge-transfer processes in colloidal cadmium sulfide-titania and cadmium sulfide-silver(I) iodide systems

Synthesis, Characterization, and Catalytic Applications of a Palladium-Nanoparticle-Cored Dendrimer

Photophysical investigation of similarities between starburst dendrimers and anionic micelles

Nanoparticle-cored dendrimers: synthesis and characterization.

Cu(II)-mediated generation of triarylamine radical cations and their dimerization. an easy route to tetraarylbenzidines.