Oxygen Reduction Reaction with Manganese Oxide Nanospheres in Microbial Fuel Cells.

Operating microbial fuel cells (MFCs) under extreme pH conditions offers a substantial benefit. Acidic conditions suppress the growth of undesirable methanogens and increase redox potential for oxygen reduction reactions (ORRs), and alkaline conditions increase the electrocatalytic activity. However, operating any fuel cells, including MFCs, is difficult under such extreme pH conditions.

Diffusion doping of cobalt in rod-shape anatase TiO nanocrystals leads to antiferromagnetism.

Cobalt(ii) ions were adsorbed to the surface of rod-shape anatase TiO nanocrystals and subsequently heated to promote ion diffusion into the nanocrystal. After removal of any remaining surface bound cobalt, a sample consisting of strictly cobalt-doped TiO was obtained and characterized with powder X-ray diffraction, transmission electron microscopy, UV-visible spectroscopy, fluorescence spectroscopy, X-ray photoelectron spectroscopy, SQUID magnetometry, and inductively-coupled plasma atomic emission spectroscopy. The nanocrystal morphology was unchanged in the process and no new crystal phases were detected.

Quantitative Attachment of Bimetal Combinations of Transition-Metal Ions to the Surface of TiO Nanorods.

We report the sequential, quantitative loading of transition-metal ions (Cr, Mn, Fe, Co, Ni, and Cu) onto the surface of rod-shaped anatase TiO nanocrystals in bimetallic combinations ( C = 15) to form M,M'-TiO nanocrystals. The materials were characterized with transmission electron microscopy (TEM), powder X-ray diffraction (XRD), elemental analysis, X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy. TEM and XRD data indicate that the sequential adsorption of metal ions occurs with the retention of the phase and morphology of the nanocrystal.

Direct arylation catalysis with chloro[8-(dimesitylboryl)quinoline-κN]copper(I).

We report direct arylation of arylhalides with unactivated sp C-H bonds in benzene and naphthalene using a copper(I) catalyst featuring an ambiphilic ligand, (quinolin-8-yl)dimesitylborane. Direct arylation could be achieved with 0.2 mol % catalyst and 3 equivalents of base (KO(-Bu)) at 80 °C to afford TON ≈160-190 over 40 hours.

Crystal structure of 8-iodo-quinolinium tetra-chlorido-aurate(III).

The structure of the title salt, (C9H7IN)[AuCl4], is comprised of planar 8-iodo-quinolinium cations (r.m.s.

Crystal structure of bis-(3-bromo-mesit-yl)(quino-lin-1-ium-8-yl)boron(III) tribromide.

The title compound, C27H26.82BBr2.18N(+)·Br3 (-), is a cationic tri-aryl-borane isolated as its tribromide salt.

Self-limiting adsorption of Eu³⁺ on the surface of rod-shape anatase TiO₂ nanocrystals and post-synthetic sensitization of the europium-based emission.

The surface of oleic acid stabilized rod-shape anatase TiO2 nanocrystals was modified by adsorption of Eu(3+) ions. The Eu(3+) attachment showed Langmuir adsorption behavior, thus the loading of Eu(3+) could be controlled precisely up to surface saturation coverage. The Eu(3+)-TiO2 nanorods show weak Eu(3+) based luminescence.

Chloro({2-[mesityl(quinolin-8-yl-κN)boryl]-3,5-dimethyl-phenyl}methyl-κC)palladium(II) as a catalyst for Heck reactions.

We recently reported an air and moisture stable 16-electron borapalladacycle formed upon combination of 8-quinolyldimesitylborane with bis(benzonitrile)dichloropalladium(II). The complex features a tucked mesityl group formed upon metalation of an ortho-methyl group on a mesityl; however it is unusually stable due to contribution of the boron pz orbital in delocalizing the carbanion that gives rise to an η4-boratabutadiene fragment coordinated to Pd(II), as evidenced from crystallographic data. This complex was observed to be a highly active catalyst for the Heck reaction.

Facile method to attach transition metal ions to the surface of anatase TiO(2) nanorods.

We report a robust, low-cost method to attach transition metal ions directly to the surface of anatase TiO2 rod-shaped nanocrystals with preservation of the host nanocrystal morphology and phase. The procedure has been optimized to achieve quantitative control of metal ion loading on the surface of the nanorods. The metal ion can be attached to the nanocrystal surface up to fullmonolayer coverage, after which the surface becomes saturated and there is no further addition.

Preparation of RHgCl via transmetalation of (8-quinolyl)SnMe₃ and redistribution to R₂Hg (R = 8-quinolyl): a highly distorted diorganomercury(II) with 84 degree C-Hg-C angle.

Transmetalation occurs upon addition of HgCl2 to (8-quinolyl)SnMe3 to yield (8-quinolyl)HgCl. The molecule features a frustrated Hg-N Lewis pair; however the mercury(II) center showed low affinity for sulfur Lewis bases, S8 or thiophene. In the presence of NH4SCN, ligand redistribution led to R2Hg.

Photoinduced Charge Transfer from Titania to Surface Doping Site.

We evaluate a theoretical model in which Ru is substituting for Ti at the (100) surface of anatase TiO. Charge transfer from the photo-excited TiO substrate to the catalytic site triggers the photo-catalytic event (such as water oxidation or reduction half-reaction). We perform computational modeling of the charge transfer dynamics on the interface of TiO nanorod and catalytic site.

1,2-Nucleophilic addition of 2-(picolyl)organoboranes to nitrile, aldehyde, ketone, and amide.

A series of 2-(picolyl)borane molecules were synthesized as products of the reaction between 2-(picolyl)lithium and R(2)BOMe (R = ethyl, 9-BBN, phenyl, 9-borafluorenyl). The 2-(picolyl)boranes were dimeric; whereas, monomers coordinated to LiOMe could be isolated when the synthesis was carried out in the presence of TMEDA and THF. The 2-(picolyl)boranes undergo reaction with nitriles, ketones, aldehydes, and amides with apparent 1,2-addition of the B-C(picolyl) bond to the unsaturated bond.

Reactivity of the bifunctional ambiphilic molecule 8-(dimesitylboryl)quinoline: hydrolysis and coordination to Cu(I), Ag(I) and Pd(II).

The ambiphilic molecule 8-(dimesitylboryl)quinoline (1) was synthesized by treatment of 8-bromoquinoline or 8-iodoquinoline with n-BuLi followed by dimesitylboronfluoride. Hydrolysis of 1 is unusually rapid compared to bulky triorganoboranes with the sequential loss of mesitylene and formation of mesityl(quinolin-8-yl)borinic acid (2) and 8-quinoline boronic acid dimer (3). Cooperativity within the bifunctional ambiphilic site leads to water activation and protodeboronation of the B-C(Mes) bonds.

Oxybis(dimesitylborane) dichloro-methane hemisolvate.

The title compound, C(36)H(44)B(2)O·0.5CH(2)Cl(2), contains an almost linear O-B-O linkage [177.23 (15)°] and approximately orthogonal [interplanar angles 89.

Bis(μ-dimesitylborinato-κO:O)bis-[(2-methyl-pyridine-κN)lithium].

The title compound, [Li(2)(C(18)H(22)BO)(2)(C(6)H(7)N)(2)], is a lithium dimesitylboroxide dimer in which the lithium cation is also coordinated by one mol-ecule of 2-methyl-pyridine. At the core of the structure is an Li(2)O(2) four-membered ring. The structure is centrosymmetric with an inversion centre midway between two Li atoms.

Fluoride ion complexation by a B(2)/Hg heteronuclear tridentate Lewis acid.

The reaction of [Li(THF)(4)][1,8-mu-(Mes(2)B)C(10)H(6)] with HgCl(2) affords [1,1'-(Hg)-[8-(Mes(2)B)C(10)H(6)](2)] () or [1-(ClHg)-8-(Mes(2)B)C(10)H(6)] (), depending on the stoichiometry of the reagents. These two new compounds have been characterized by (1)H, (13)C, (11)B and (199)Hg NMR, elemental analysis and X-ray crystallography. The cyclic voltammogram of in THF shows two distinct waves observed at E(1/2) -2.

8-Iodo-quinolinium triiodide tetra-hydro-furan solvate.

The title compound, C(9)H(7)IN(+)·I(3) (-)·C(4)H(8)O, was synthesized from 8-amino-quinoline using the Sandmeyer reaction. The 8-iodo-quinolinium cation is essentially planar and the triiodide ion is almost linear. N-H⋯O hydrogen bonds, and inter-molecular I⋯I [3.

8-Iodo-quinolinium chloride dihydrate.

The title compound, C(9)H(7)IN(+)·Cl(-)·2H(2)O, was obtained during the synthesis of 8-iodo-quinoline from 8-amino-quinoline using the Sandmeyer reaction. The 8-iodo-quinolinium ion is almost planar. Solvent water mol-ecules and chloride ions form a hydrogen-bonded chain along the c axis via O-H⋯Cl links.

Adsorption and co-adsorption of ethylene and carbon monoxide on silica-supported monodisperse Pt nanoparticles: volumetric adsorption and infrared spectroscopy studies.

The adsorption of carbon monoxide and ethylene, and their sequential adsorption, was studied over a series of Pt/SBA-15 catalysts with monodisperse particle sizes ranging from 1.7 to 7.1 nm by diffuse-reflectance infrared spectroscopy and chemisorption.

Reverse micelle synthesis of rhodium nanoparticles.

Water-in-oil reverse micelles of butyl ammonium laurate in hexanes that contain sodium hexachlororhodate were reduced with sodium borohydride to yield rhodium nanoparticles. The size of the micelle, determined by dynamic light scattering, was from 3 to 20 nm and varied as the water to surfactant ratio (W) was changed. The rhodium nanoparticles exhibited a Gaussian size distribution (sigma=0.

Hydrothermal growth of mesoporous SBA-15 silica in the presence of PVP-stabilized Pt nanoparticles: synthesis, characterization, and catalytic properties.

A novel high surface area heterogeneous catalyst based on solution phase colloidal nanoparticle chemistry has been developed. Monodisperse platinum nanoparticles of 1.7-7.

Radial anisotropic growth of rhodium nanoparticles.

In this contribution, we report the synthesis of rhodium multipods that result from a homogeneous seeded growth mechanism. Small Rh nanocrystal seeds were synthesized by the reduction of RhCl3 in ethylene glycol in the presence of PVP. These seed particles could be subsequently used, without isolation, to form larger rhodium nanoparticles.

Reactivity of the dimesityl-1,8-naphthalenediylborate anion: isolation of the borataalkene isomer and synthesis of 1,8-diborylnaphthalenes.

The anionic boron peri-bridged naphthalene derivative, namely dimesityl-1,8-naphthalenediylborate (1), undergoes a hydrolysis reaction to afford dimesityl-1-naphthylborane (2) whose structure has been determined. Upon standing at room temperature in toluene for an extended period of time, 1 undergoes a ring expansion reaction to afford 8,10,11a-trimethyl-7-mesityl-11aH-7-boratabenzo[de]anthracene (3). As shown by its crystal structure, compound 3 constitutes a rare example of a borataalkene and features a carbon-boron double bond of 1.

Cooperative effects in the complexation of anions and Lewis bases by a heteronuclear bifunctional Lewis acid.

As shown by the complexation of electron-rich substrates to the heteronuclear bifunctional Lewis acid bis(mu-1,8-naphthalenediyl)(mu-chloride)methyltin-chlorogallium (1), the primary Lewis acidic site of this molecule is the triorganotin chloride moiety whose electron deficiency is enhanced through partial abstraction of its chloride ligand by the neighbouring gallium centre.