There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality.

Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

I and i

Two organolead halide perovskite nanocrystals, CH3NH3PbBr3 and CH3NH3PbI3, were found to efficiently sensitize TiO2 for visible-light conversion in photoelectrochemical cells. When self-assembled on mesoporous TiO2 films, the nanocrystalline perovskites exhibit strong band-gap absorptions as semiconductors. The CH3NH3PbI3-based photocell with spectral sensitivity of up to 800 nm yielded a solar energy conversion efficiency of 3.8%. The CH3NH3PbBr3-based cell showed a high photovoltage of 0.96 V with an external quantum conversion efficiency of 65%.

Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells

Single-layer metal dichalcogenides are two-dimensional semiconductors that present strong potential for electronic and sensing applications complementary to that of graphene.

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Electronics and optoelectronics of two-dimensional transition metal dichalcogenides.

Although gold is the subject of one of the most ancient themes of investigation in science, its renaissance now leads to an exponentially increasing number of publications, especially in the context of emerging nanoscience and nanotechnology with nanoparticles and self-assembled monolayers (SAMs). We will limit the present review to gold nanoparticles (AuNPs), also called gold colloids. AuNPs are the most stable metal nanoparticles, and they present fascinating aspects such as their assembly of multiple types involving materials science, the behavior of the individual particles, size-related electronic, magnetic and optical properties (quantum size effect), and their applications to catalysis and biology. Their promises are in these fields as well as in the bottom-up approach of nanotechnology, and they will be key materials and building block in the 21st century. Whereas the extraction of gold started in the 5th millennium B.C. near Varna (Bulgaria) and reached 10 tons per year in Egypt around 1200-1300 B.C. when the marvelous statue of Touthankamon was constructed, it is probable that “soluble” gold appeared around the 5th or 4th century B.C. in Egypt and China. In antiquity, materials were used in an ecological sense for both aesthetic and curative purposes. Colloidal gold was used to make ruby glass 293 Chem. Rev. 2004, 104, 293−346

Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology.

To use solar irradiation or interior lighting efficiently, we sought a photocatalyst with high reactivity under visible light. Films and powders of TiO 2- x N x have revealed an improvement over titanium dioxide (TiO 2 ) under visible light (wavelength 2 has proven to be indispensable for band-gap narrowing and photocatalytic activity, as assessed by first-principles calculations and x-ray photoemission spectroscopy.

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Visible-Light Photocatalysis in Nitrogen-Doped Titanium Oxides

Two-dimensional (2D) lead halide perovskites with better chemical stability and tunable dimensionality offer new opportunities to design optoelectronic devices. We have probed the transient absorpt...

Charge Carrier Recombination Dynamics of Two-Dimensional Lead Halide Perovskites

Oxidative transformations by the hydroxyl radical are significant in advanced oxidation processes for the breakdown of organic pollutants, yet mechanistic details of the reactions are lacking. A combination of experimental and computational methods has been employed in this study to elucidate the reactivity of the hydroxyl radical with the widely used herbicide 2,4-D (2,4-dichlorophenoxyacetic acid). The experimental data on the reactivity of the hydroxyl radical in the degradation of the herbicide 2,4-D were obtained from gamma-radiolysis experiments with both (18)O-labeled and unlabeled water. These were complemented by computational studies of the (.)OH attack on 2,4-D and 2,4-DCP (2,4-dichlorophenol) in the gas phase and in solution. These studies firmly established the kinetically controlled attack ipso to the ether functionality as the main reaction pathway of (.)OH and 2,4-D, followed by homolytic elimination of the ether side chain. In addition, the majority of the early intermediates in the reaction between the hydroxyl radical and 2,4-DCP, the major intermediate, were identified experimentally. While the hydroxyl radical attacks 2,4-D by (.)OH-addition/elimination on the aromatic ring, the oxidative breakdown of 2,4-DCP occurs through (.)OH addition followed by either elimination of chlorine or formation of the ensuing dichlorophenoxyl radical.

Mechanism of Hydroxyl Radical‐Induced Breakdown of the Herbicide 2,4‐Dichlorophenoxyacetic Acid (2,4‐D)

β-Cyclodextrin (β-CD) forms a 2: 1 inclusion complex with the anion of bis(2,4,6-trihydroxyphenyl)squaraine dye (Sq), in aqueous solutions, bringing about a significant enhancement in the fluorescence yield (ca. 90-fold) and the stability of the dye anion. Apart from the effect of the hydrophobic environment and the decrease in rotational freedom brought about by β-CD encapsulation, intramolecular hydrogen bonding between the OH groups on the phenyl rings and the oxygen atoms in the central cyclobutane ring in the anion guest molecule can significantly contribute to the stiffening of the molecule in the excited state. In the absence of β-CD, intermolecular hydrogen bonding with solvent molecules disrupts the intramolecular hydrogen-bonding processes, bringing about a decrease in the fluorescence yield of the anion.

Fluorescence enhancement of bis(2,4,6-trihydroxyphenyl)squaraine anion by 2 : 1 host–guest complexation with β-cyclodextrin

The singlet and triplet lifetimes of erythrosin B and rose bengal, two representative xanthene dyes, are significantly increased by enclosing the dye in a cage of poly(4-vinylpyridine) (PVP). The fluorescence yield, controlled by the rate of intersystem crossing, is also increased by such encapsulation. Parallel effects are observed upon adding the polymer to an ethanolic solution of the xanthene or upon loading the dye into a polymer matrix dispersed on a metal oxide surface. The effect of the polymer on static quenching of the excited dye and the implications of dye-loaded polymer films in solar energy conversion are discussed.

Photophysics and photochemistry of xanthene dyes in polymer solutions and films

Reduced graphene oxide (RGO) has become a common substrate upon which active intercalation materials are anchored for electrochemical applications such as supercapacitors and lithium ion batteries. The unique attributes of RGO, including high conductivity and porous macrostructure, are often credited for enhanced cycling and capacity performance. Here we focus on probing the electrochemical response of α-MnO2/RGO composite used as an electrode in a lithium ion battery cell and elucidating the mechanistic aspects of the RGO on the commonly observed improvements in cycling and capacity. We find that electron storage properties of RGO enables better electrode kinetics, more rapid diffusion of Li+ to intercalation sites, and a greater capacitance effect during discharge. Further investigation of the length of the one-dimensional nanowire morphology of the α-MnO2 has allowed us to differentiate between the innate characteristics of the MnO2 and those of the RGO. RGO coupled with long nanowires (>5 μm) exhibite...

Prashant V. Kamat

Papers

Charge Carrier Recombination Dynamics of Two-Dimensional Lead Halide Perovskites

Mechanism of Hydroxyl Radical‐Induced Breakdown of the Herbicide 2,4‐Dichlorophenoxyacetic Acid (2,4‐D)

Fluorescence enhancement of bis(2,4,6-trihydroxyphenyl)squaraine anion by 2 : 1 host–guest complexation with β-cyclodextrin

Photophysics and photochemistry of xanthene dyes in polymer solutions and films

Origin of Reduced Graphene Oxide Enhancements in Electrochemical Energy Storage