Insights into electrochemical behavior and kinetics of NiP on PEDOT:PSS/reduced graphene oxide as high-performance electrodes for alkaline urea oxidation

Journal of Solid State Electrochemistry - Highly efficient, abundant, and low-cost materials are highly demanded for energy conversion applications to address the rising consumption of energy. In...     

A Phosphorescent Platinum(II) Bipyridyl Supramolecular Polymer Based on Quadruple Hydrogen Bonds

A platinum(II) bipyridyl complex bearing bis‐ureidopyrimidinone (Pt‐bisUPy) has been designed and its self‐assembling behavior has been thoroughly investigated by ¹H NMR, DOSY NMR, Ubbelohde viscometry analysis, UV/Vis, and emission spectroscopies. Pt‐bisUPy underwent concentration‐dependent ring‐chain polymerization in apolar solvents. Hydrogen‐bonding interactions play an important role during the formation of the supramolecular polymers. Hydrogen‐bonded supramolecular polymers were transformed to nanoparticles in water through the miniemulsion method. These nanoparticles showed strong π–π excimeric emission. Metal‐metal‐to‐ligand charge transfer (MMLCT) from Pt–Pt interactions was not significant in the emission spectrum. The phosphorescence of the nanoparticle persisted even under aerobic conditions. The triplet state of these phosphorescent nanomaterials were long‐lived and possessed moderate emission quantum yields. Furthermore, the low toxicity of these materials promises a place for them in in vitro and in vivo bioimaging.     

Spatial confinement alters the ultrafast photoisomerization dynamics of azobenzenes

Ultrafast transient absorption spectroscopy reveals new excited-state dynamics following excitation of trans-azobenzene (t-Az) and several alkyl-substituted t-Az derivatives encapsulated in a water-soluble supramolecular host–guest complex. Encapsulation increases the excited-state lifetimes and alters the yields of the trans → cis photoisomerization reaction compared with solution. Kinetic modeling of the transient spectra for unsubstituted t-Az following nπ* and ππ* excitation reveals steric trapping of excited-state species, as well as an adiabatic excited-state trans → cis isomerization pathway for confined molecules that is not observed in solution. Analysis of the transient spectra following ππ* excitation for a series of 4-alkyl and 4,4′-dialkyl substituted t-Az molecules suggests that additional crowding due to lengthening of the alkyl tails results in deeper trapping of the excited-state species, including distorted trans and cis structures. The variation of the dynamics due to crowding in the confined environment provides new evidence to explain the violation of Kasha''s rule for nπ* and ππ* excitation of azobenzenes based on competition between in-plane inversion and out-of-plane rotation channels.

Ultrafast transient absorption spectroscopy reveals new excited-state dynamics following excitation of trans-azobenzene (t-Az) and several alkyl-substituted t-Az derivatives encapsulated in a water-soluble supramolecular host–guest complex.     

An Ultra-Microporous Metal–Organic Framework with Exceptional Xe Capacity

Molecular confinement plays a significant effect on trapped gas and solvent molecules. A fundamental understanding of gas adsorption within the porous confinement provides information necessary to design a material with improved selectivity. In this regard, metal–organic framework (MOF) adsorbents are ideal candidate materials to study confinement effects for weakly interacting gas molecules, such as noble gases. Among the noble gases, xenon (Xe) has practical applications in the medical, automotive and aerospace industries. In this Communication, we report an ultra-microporous nickel-isonicotinate MOF with exceptional Xe uptake and selectivity compared to all benchmark MOF and porous organic cage materials. The selectivity arises because of the near perfect fit of the atomic Xe inside the porous confinement. Notably, at low partial pressure, the Ni–MOF interacts very strongly with Xe compared to the closely related Krypton gas (Kr) and more polarizable CO₂. Further ¹²⁹Xe NMR suggests a broad isotropic chemical shift due to the reduced motion as a result of confinement.     

Comparison of Templating Abilities of Urea and Thioruea During Photodimerization of Bipyridylethyelene and Stilbazole Crystals

Photodimerization of cocrystals of four bispyridylethylenes and two stilbazoles with urea as a template in the solid state has been investigated following our success with thiourea. Four investigated olefins photodimerized quantitatively to a single dimer in the crystalline state only. The reactivity of urea–olefin crystals is understood on the basis of their packing arrangements in the crystalline state. In reactive crystals the adjacent reactive molecules are within 4.2 Å and parallel, whereas the unreactive ones have their adjacent molecules are farther than 4.6Å and nonparallel. Thus, with the knowledge of crystal packing the reactivity of urea–olefin crystals is predictable on the basis of Schmidt's topochemical postulates. The templating property of urea, similar to thiourea, derives from its ability to form hydrogen bonds with itself and the guest olefins. Despite the similarities in molecular structures of urea and thiourea their subtle electronic properties, yet to be fully understood, affect the crystal packing and consequently their reactivity in the crystalline state. Further work is needed to fully exploit the templating properties of urea.     

Proton coupled electron transfer reaction of phenols with excited state ruthenium(II) – polypyridyl complexes

The reaction of phenols with the excited state, *[Ru(bpy)₃]²⁺ (E₀ = 0.76 V) and *[Ru(H₂dcbpy)₃]²⁺, (dcbpy = 4,4′‐dicarboxy‐2,2′‐bipyridine) (E₀ = 1.55 V vs. SCE) complexes in CH₃CN has been studied by luminescence quenching technique and the quenching is dynamic. The formation of phenoxyl radical as a transient is confirmed by its characteristic absorption at 400 nm. The k_q value is highly sensitive to the change of pH of the medium and ΔG⁰ of the reaction. Based on the treatment of k_q data in terms of energetics of the reaction and pH of the medium, proton coupled electron transfer (PCET) mechanism has been proposed for the reaction. Copyright © 2010 John Wiley & Sons, Ltd.     

Gold Decorated Graphene by Laser Ablation for Efficient Electrocatalytic Oxidation of Methanol and Ethanol

A well‐known limitation in the fabrication of metal‐graphene composite has been the use of surfactants that strongly adsorb on the surface and reduce the performance of the catalyst. We demonstrate here a novel one‐pot synthesis of gold nanoparticles by laser ablation of gold strip and in‐situ decoration on graphene substrate. Not only the impregnation of nanoparticles was linker free, but also the synthesis by itself was surfactant‐free. The composite materials were well characterized morphologically and functionally using electron microscopy, X‐ray and electron diffraction, Raman spectroscopy, Zeta potential, electrochemical measurements and UV‐Visible spectroscopic techniques. This linker‐free gold‐graphene based composite has been employed for catalytic applications pertaining to electrooxidation. We have explored the use of this composite as a binder‐free electrode in electrocatalytic oxidation of methanol and ethanol in alkaline medium. Additionally, the onset potential for ethanol oxidation was found to be more negative, ?100 mV, an indication of its promising application in direct ethanol fuel cells.     

Experimental signature of entrance channel effect in heavy mass region via evaporation residue cross section and spin distribution measurements

Evaporation residue (ER) cross sections and gamma multiplicity distributions have been measured for ¹⁶O + ¹⁸⁴W and ¹⁹F + ¹⁸¹Ta systems in the excitation energy range of 50–90 MeV, leading to the same compound nucleus ²⁰⁰Pb^∗. Comparison of experimental results of both the systems shows that ER cross sections and moments of gamma multiplicity distribution of ¹⁶O + ¹⁸⁴W system are significantly higher than those of ¹⁹F + ¹⁸¹Ta system at higher excitation energies. Present measurements directly shows the experimental signature of entrance channel effect even with the systems which are not very different with respect to their entrance channel mass asymmetry. It is further demonstrated that the reduction in the ER cross section and moments of spin distribution for ¹⁹F + ¹⁸¹Ta system is mainly due to the suppression of fusion of higher l values.