Boosting Hydrogen Evolution at Visible Light Wavelengths by Using a Photocathode with Modal Strong Coupling between Plasmons and a Fabry-Pérot Nanocavity

Hot-hole injection from plasmonic metal nanoparticles to the valence band of p-type semiconductors and reduction by hot electrons should be improved for efficient and tuneable reduction to obtain beneficial chemical compounds. We employed the concept of modal strong coupling between plasmons and a Fabry-Pérot (FP) nanocavity to enhance the hot-hole injection efficiency. We fabricated a photocathode composed of gold nanoparticles (Au−NPs), p-type nickel oxide (NiO), and a platinum film (Pt film) (ANP). The ANP structure absorbs visible light over a broad wavelength range from 500 nm to 850 nm via hybrid modes based on the modal strong coupling between the plasmons of Au−NPs and the FP nanocavity of NiO on a Pt film. All wavelength regions of the hybrid modes of the modal strong coupling system promoted hot-hole injection from the Au−NPs to NiO and proton/water reduction by hot electrons. The incident photon-to-current efficiency based on H₂ evolution through water/proton reduction by hot electrons reached 0.2 % at 650 nm and 0.04 % at 800 nm.     

Flexible Alkylene Bridges as a Tool To Engineer Crystal Distyrylbenzene Structures Enabling Highly Fluorescent Monomeric Emission

To design ultrabright fluorescent solid dyes, a crystal engineering strategy that enables monomeric emission by blocking intermolecular electronic interactions is required. We introduced propylene moieties to distyrylbenzene (DSB) as bridges between the phenyl rings either side of its C=C bonds. The bridged DSB derivatives formed compact crystals that emit colors similar to those of the same molecules in dilute solution, with high quantum yields. The introduction of flexible seven-membered rings to the DSB core produced moderate distortion and steric hindrance in the DSB π-plane. However, owing to this strategy, it was possible to control the molecular arrangement with almost no decrease in the crystal density, and intermolecular electronic interactions were suppressed. The bridged DSB crystal structure differs from other DSB derivative structures; thus, bridging affords access to novel crystalline systems. This design strategy has important implications in many fields and is more effective than the conventional photofunctional molecular crystal design strategies.     

New fabrication approach to develop a high birefringence photo-crosslinked film based on a sulfur-containing liquid crystalline molecule with large temperature dependence of birefringence

ABSTRACT

We present a new fabrication approach to achieve a high birefringence film by means of photopolymerization based on an alkylthio-containing rod-like liquid crystalline molecule exhibiting large temperature dependence of birefringence. We designed a new reactive mesogen having alkylthio linkages (BPM–S). It was found that BPM–S had a larger increment of birefringence with decreasing temperature, relative to commercially available alkoxy analog LC242. This result could be thought to be due to enhanced intermolecular attractive interaction for an alkylthio mesogen implied by the proximity of laterally neighboring molecules and cybotactic nematic tendency based on wide-angle X-ray measurement. The uniaxially-aligned photo-polymerized film for BPM–S showed higher birefringence than that for LC 242.     

Plasmon‐Induced Water Splitting Using Metallic‐Nanoparticle‐Loaded Photocatalysts and Photoelectrodes

The front cover artwork is provided by the group of Prof. Hiroaki Misawa (Hokkaido University, Japan, and National Chiao Tung University, Taiwan). The image shows a plasmon‐induced water‐splitting system, which can collect hydrogen and oxygen separately and employs a semiconductor substrate. Read the full text of the Review at 10.1002/cphc.201500761     

Anionic polymerization of N,N‐dialkyl‐2‐methylenebut‐3‐enamide: Effect of alkyl substituents on polymerization behavior

Anionic polymerizations of three 1,3‐butadiene derivatives containing different N,N‐dialkyl amide functions, N,N‐diisopropylamide (DiPA), piperidineamide (PiA), and cis‐2,6‐dimethylpiperidineamide (DMPA) were performed under various conditions, and their polymerization behavior was compared with that of N,N‐diethylamide analogue (DEA), which was previously reported. When polymerization of DiPA was performed at ?78 °C with potassium counter ion, only trace amounts of oligomers were formed, whereas polymers with a narrow molecular weight distribution were obtained in moderate yield when DiPA was polymerized at 0 °C in the presence of LiCl. Decrease in molecular weight and broadening of molecular weight distribution were observed when polymerization was performed at a higher temperature of 20 °C, presumably because of the effect of ceiling temperature. In the case of DMPA, no polymer was formed at 0 °C and polymers with relatively broad molecular weight distributions (M_w/M_n = 1.2) were obtained at 20 °C. The polymerization rate of PiA was much faster than that of the other monomers, and poly(PiA) was obtained in high yield even at ?78 °C in 24 h. The microstructure of the resulting polymers were exclusively 1,4‐ for poly(DMPA), whereas 20–30% of the 1,2‐structure was contained in poly(DiPA) and poly(PiA). © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3714–3721, 2010     

Mean curvature functions of codimension-one foliations

The author is partially supported by a grant from the Alexander von Humboldt Foundation.     

A new method for the synthesis of α-arylalkanoic acids by the use of 1,2-rearrangement of the aryl group

A simple synthetic method of α-arylalkanoic acids was accomplished by the use of a novel 1,2-rearrangement of the aryl group and this method was applied to the syntheses of some biologically important substances.     

Water molecule adsorption properties on the BiVO4 (100) surface

The water absorption properties at the surface of BiVO4 are attracting a great deal of attention because the system is a promising candidate as a photocatalyst operating in the visible light range. This has motivated the present investigation via first principles molecular dynamics, which has revealed that a H2O molecule is adsorbed molecularly, instead of dissociatively, at the fivefold Bi site with an adsorption energy of approximately 0.58 eV/molecule. The band gap of the system shrinks slightly (by approximately 0.2 eV) upon water adsorption and it is likely that oxygen atoms belonging to the adsorbed water molecules to the Bi sites are oxidized, as inferred by the small Bi-Owater equilibrium distance (approximately 2.6-2.8 A) very close to the Bi-O bond in the bulk crystal. In the case of water adsorption at a Bi site, the distance between Hwater and V, which is a reduction site, is larger than in the case of adsorption at a V site, indicating that the proton reduction processes may be suppressed.