An innovative BASF catalyst manufacturing technology (NanoSelect TM ) is introduced which allows production of heterogeneous catalysts with excellent control over metal crystallite sizes. NanoSelect TM technology enabled the development of Pd catalysts which are leadfree Lindlar catalyst replacements in alkyne-to-cis-alkene hydrogenations. NanoSelect TM Pt catalysts showed excellent chemoselectivity in substituted nitro-arene hydrogenation reactions without build-up of hydroxylamine intermediates. All NanoSelect TM produced catalysts show markedly higher activity per gram of metal leading to tenfold less use of precious metal.
The production of stable redox-active layers on electrode surfaces can lead to improvements in electronic device design. Enhanced stability can be achieved by pretreatment of electrode surfaces to provide surface chemical functional groups for covalent tethering of redox complexes. Herein, we describe pretreatment of glassy carbon electrodes to provide surface carboxylic acid groups by electro-reduction of an in situ-generated aryl diazonium salt from 3-(4-aminophenyl)propionic acid. This surface layer is characterized by attenuated total reflection infrared spectroscopy, atomic force microscopy, and electrochemical blocking studies. The surface carboxylic acid generated is then used to tether an osmium complex, [Os(2,2'-bipyridyl)2(4-aminomethylpyridine)Cl]PF6, to provide a covalently bound redox-active monolayer, E(0) ' of 0.29 V (vs Ag/AgCl in phosphate buffer, pH 7.4), on the pretreated glassy carbon electrode. The layer proves stable to pH, temperature, and storage conditions, retaining electroactivity for at least 6 months.
In recent years, many articles describing the preparation of supported colloidal catalysts have been published. The semi‐hydrogenation of alkynes to yield cis‐alkenes is often used as a test reaction in these publications. Many highly selective catalysts are described. However, a satisfactory explanation for the high reported selectivity has never been shown. Here we report a study on the possible effects that lead to the large selectivity differences between current commercial Pd/C catalysts and our newly developed NanoSelect catalysts. The focus is on differences in chemical composition as well as catalyst characteristics. We use a focused ion beam scanning electron microscope (FIB‐SEM) to locate the metal particle with respect to the surface of the support. FIB‐SEM analysis clearly shows the absence of the active component inside the support material, which could explain the high observed selectivity. Nevertheless, an effect of the stabilizer cannot be ruled out.
Positive discrimination: Supported MoVI promoted Pt nanoparticles (c‐Pt+Mo/C) are successfully applied as catalysts in the chemoselective hydrogenation of functionalized nitroarenes. Mild conditions (30 °C, 4 bar H2, EtOH) prove sufficient for complete reduction to the corresponding anilines, leaving other functional groups untouched. Turnover numbers of at least 20 000 show that this catalyst is very tolerant to halogen‐containing aromatics.
We report on the performance of a prototype glucose/O2 biofuel cell in a physiological buffer. The cell consists of cathode based on Melanocarpus albomyces laccase (with a reported T1 copper redox potential of + 0.26 V vs. Ag/AgCl) co‐immobilised with an osmium redox polymer mediating film on glassy carbon (GC) separated by a Nafion 117 membrane from a GC anode in anolyte of glucose oxidase, N,N,N′,N′‐tetramethyl‐p‐phenylenediamine (TMPD) as a mediator, all immersed in pH 7.4 phosphate buffer solution containing 0.15 M NaCl and dissolved oxygen, thermostated at 37 °C, mimicking physiological conditions. Two osmium redox polymers are employed for cathodic mediation: [Os(2,2′‐bipyridine)2(polyvinylimidazole)10Cl]+/2+ (E°′ 0.22 V vs. Ag/AgCl) and [Os(4,4′‐dichloro‐2,2′‐bipyridine)2(polyvinylimidazole)10Cl]+/2+ (E°′ 0.35 V vs. Ag/AgCl). Power outputs of 52 μW cm–2 at 0.21 V and 17 μW cm–2 at 0.34 V were obtained for assembled fuel cells containing the respective redox polymer‐mediated laccase cathodes, illustrating the increased power obtained as a result of higher biocatalytic efficiency using a redox polymer with redox potential tailored for the enzyme.
Highly ordered macroporous electrodes are prepared by electro-deposition of gold through a polystyrene sphere template. Drop-coating redox polymer and either glucose oxidase, for the anode, or Melanocarpus albomyces laccase, for the cathode on the macroporous gold provides film-coated electrodes for assembly of membrane-less glucose/oxygen enzymatic fuel cells (EFC) in pH 7.4 buffer containing 10 mM glucose and 0.15 M NaCl. Under these conditions the maximum power density of 17 μW cm(-2) for EFCs using films adsorbed to planar gold electrodes increased to 38 μW cm(-2) for films adsorbed to 2½ sphere gold macroporous electrodes.
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