Unraveling the synergy between gold nanoparticles and chromium- hydrotalcites in aerobic oxidation of alcohols

The combination of gold nanoparticles (AuNPs) with chromium-substituted hydrotalcite (Cr-HT) supports makes very efficient heterogeneous catalysts (Au/Cr-HT) for aerobic alcohol oxidation under soluble-base-free conditions. The Au-support synergy increases with increasing Cr content of the support and decreasing AuNP size. In situ UV-Raman, X-ray absorption and photoelectron spectroscopic studies firmly establish that the strong Au-Cr synergy is related to a Cr ↔ Cr redox cycle at the Au/Cr-HT interface, where O activation takes place accompanied by electron transfer from Cr-HT to Au. The interfacial Cr species can be reduced by surface Au-H hydride and negative-charged Au species to close the catalytic cycle. A study of kinetic isotope effect indicates that alcohol O-H cleavage is facilitated by the presence of Cr, making a-C-H bond cleavage step more rate-controlling. Accordingly, a dual synergistic effect of Au/Cr-HT catalysts on the activation of O2 and alcohol reactants is proposed.

Selective Palladium-Catalysed Aerobic Oxidation of Alcohols

Palladium has a significant track record as a catalyst for a range of oxidation reactions and it has been explored for the selective oxidation of alcohols for many years. This chapter focuses on the two main types of aerobic Pd catalysts: heterogeneous and ligand-modulated systems. In the case of heterogeneous systems, the mechanistic understanding of these systems and the use of in situ and operando techniques to obtain this knowledge are discussed. The current state-of-the-art is also summarized in terms of catalytic performance and substrate scope for heterogeneous Pd-based catalysts. In terms of ligand-modulated systems, leading examples of molecular Pd(ii) catalysts which undergo direct O2 coupled turnover are highlighted. The catalyst performance for such catalysts is exemplified and mechanistic understanding for these molecular systems is discussed.

Containing precious metals: hallmarking, minting and the materiality of gold and silver in medieval and modern England.

This book chapter extends the argument constructed by Oakley in his conference paper ‘Containing gold: Institutional attempts to define and constrict the values of precious metal objects’ presented at ‘Itineraries of the Material’, a conference held at Goethe Universitaet, Frankfurt am Main in 2011. Oakley’s chapter investigates the social forces that define the identities, social pathways and physical movement of objects made of precious metal. It presents a case study in which constitutive substance rather than the conceptual object is the key driver behind the social trajectories of numerous artefacts and their reception by contemporary audiences. This supports the main contention of the book as a whole: the need to reconsider, and when necessary challenge, the dominance of the social biography of objects in the study of material culture. Oakley’s research used historical and ethnographic approaches, including three years’ of ethnographic field research in the jewellery industry. This included training as a precious metal assayer at the Birmingham Assay Office and observing the industry and public response to government proposals to abolish the hallmarking legislation. This fieldwork was augmented by archive, library and object collection research on the histories of assaying and goldsmithing. Oakley presents an analysis of the historical development and contemporary social relevance of hallmarking, a technological process that has never previously been subject to ethnographic study, yet is fundamental to one of the UK’s creative industries.

Bioinspired iron and manganese catalysts for the effective and selective oxidation of alkanes and alkenes

La gran eficiència, selectivitat i les condicions suaus exhibides per les reaccions que tenen lloc al centre actiu de les metal·looxigenases són la font d'inspiració per la present dissertació. Amb l'objectiu de dissenyar catalitzadors d'oxidació eficients hem fet ús de dues estratègies: la primera consisteix en el disseny de complexos amb baix pes molecular inspirats en aspectes estructurals de la primera esfera de coordinació del centre metàl·lic d'enzims de ferro i de manganès. Aquests complexos s'han estudiat com a catalitzadors en l'oxidació selectiva d'alcans i d'alquens fent servir oxidants "verds" com ara l'H2O2. La segona estratègia està basada en l'ús de la química supramolecular per tal de desenvolupar estructures moleculars auto-acoblades amb la forma i les propietats químiques desitjades. Concretament, la construcció de nanocontenidors amb un catalitzador d'oxidació incrustat a la seva estructura ens permetria dur a terme reaccions més selectives, tal com passa en les reaccions catalitzades per enzims.

Polymer-supported nitroxyl catalysts for selective oxidation of alcohols

Novel non-toxic poly(ethylene glycol)-supported 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) moieties are demonstrated to give an excellent interfacial catalysis for the selective oxidation of alcohols to the corresponding carbonyl species in biphasic media and investigation for the recovery of these new macromolecular catalysts via precipitation with diethyl ether after catalysis has also been briefly studied.

Synthesis of multicarboxylic acid appended imidazolium ionic liquids and their application in palladium-catalyzed selective oxidation of styrene

A series of multicarboxylic acid appended imidazolium ionic liquids ( McaILs) with chloride [ Cl](-) or bromide [ Br](-) as anions have been synthesized and characterized. Deprotonation of these ionic acids gives the corresponding zwitterions. Re-protonation of the zwitterions with strong Bronsted acids gives a series of new ionic acid-adducts, many of which remained as room-temperature ionic liquids. A new catalytic system, McaIL/PdCl2 for the selective catalytic oxidation of styrene to acetophenone with hydrogen peroxide as an oxidant has been attempted. In the presence of McaILs, it is found that the quantity of palladium chloride PdCl2 used can be greatly reduced while the activity ( TOF) and selectivity towards acetophenone are enhanced sharply. It is also shown that the catalytic properties of this system could be finely tuned through the molecular design of the McaILs. The best TOF value obtained so far is 146 h(-1) with 100% conversion of styrene at 93% selectivity to acetophenone. In addition, the catalytic activity has been maintained for at least ten catalytic cycles.

Supramolecular Approach to Gold Nanoparticle/Triruthenium Cluster Hybrid Materials and Interfaces

A systematic and comprehensive study of the interaction of citrate-stabilized gold nanoparticles with triruthenium cluster complexes of general formula [Ru(3)(CH(3)COO)(6)(L)](+) [L = 4-cyanopyridine (4-CNpy), 4,4`-bipyridine (4,4`-bpy) or 4,4`-bis(pyridyl)ethylene (bpe)] has been carried out. The cluster-nanoparticle interaction in solution and the construction of thin films of the hybrid materials were investigated in detail by electronic and surface plasmon resonance (SPR) spectroscopy, Raman scattering spectroscopy and scanning electron microscopy (SEM). Citrate-stabilized gold nanoparticles readily interacted with [Ru(3)O(CH(3)COO)(6)(L)(3)](+) complexes to generate functionalized nanoparticles that tend to aggregate according to rates and extents that depend on the bond strength defined by the characteristics of the cluster L ligands following the sequence bpe > 4,4`-bpy >> 4-CNpy. The formation of compact thin films of hybrid AuNP/[Ru(3)O(CH(3)COO)(6)(L)(3)](+) derivatives with L = bpe and 4,4`-bpy indicated that the stability/lability of AuNP-cluster bonds as well as their solubility are important parameters that influence the film contruction process. Fluorine-doped tin oxide electrodes modified with thin films of these nanomaterials exhibited similar electrocatalytic activity but much higher sensitivity than a conventional gold electrode in the oxidation of nitrite ion to nitrate depending on the bridging cluster complex, demonstrating the high potential for the development of amperometric sensors.

Selective oxidation synthesis of MnCr2O4 spinel nanowires from Commercial stainless steel foil

For the first time, MnCr₂O₄ spinel single-crystalline nanowires were simply synthesized by heating commercial stainless steel foil (Cr_0.19Fe_0.70Ni_0.11) under a reducing atmosphere. The nanowires have an average diameter of 50 nm and a length of about 10 μm. Some nanowires are sheathed with a thin layer of amorphous silicon oxide. Photoluminescence measurements revealed that the nanowires exhibit an emission band at 435 nm, which resulted from the oxygen-related defects in the silicon oxide sheath. It was found that the reducing atmosphere plays a key role for the nanowire growth. In the reducing atmosphere, the Mn and Cr elements in the stainless steel could be selectively oxidized because of their higher affinity for oxygen than the Fe and Ni elements. The Fe and Ni elements in the stainless steel, however, acted as the catalyst for the vapor–liquid–solid (VLS) growth of the MnCr₂O₄ nanowires.

Catalytic properties of nanofibrous carbon in selective oxidation of hydrogen sulphide

Nanofibrous carbonaceous materials (NFC) as a new class of materials having many applications, can catalyze the selective oxidation of H2S to sulfur. The correlation between NFC structure and its activity and selectivity in H2S oxidation was determined. It is demonstrated that selectivity can be improved if NFC with more ordered structure be synthesized and the portion of the original catalyst in carbon be reduced by increasing the carbon accumulated in the catalyst.

New effective catalysts based on mesoporous nanofibrous carbon for selective oxidation of hydrogen sulfide

The systems based on granular mesoporous nanofibrous carbonaceous (NFC) materials synthesized by decomposition of hydrocarbons over nickel- containing catalysts are promising catalysts for selective oxidation of hydrogen sulfide. Sample series of nanofibrous carbon with three main types of their fiber structures and different contents of metal catalysts inherited from the catalysts for their synthesis were studied in this reaction. The correlation between NFC structure and its activity and selectivity in hydrogen sulfide oxidation was determined. The metal inherited from the initial catalysts for the synthesis of NFC influences the activity and selectivity of the resulting carbon catalysts. A particular influence is observed in the case of the catalyst withdrawn from the synthesis reactor at the stage of stationary operation of the metal catalyst (low specific carbon yields per unit weight of the catalyst). The presence of the metal phase results in an increase in the carbon catalyst activity and in a decrease in the selectivity to sulfur. NFC samples with the highest activity and selectivity are nanotubes and those with graphite planes perpendicular to the axis of the fibers. Carbon nanotubes have high selectivity, while samples obtained on copper–nickel catalysts also possess high activity. The promising NFC catalysts provide high conversion and selectivity (almost independent of the molar oxygen/hydrogen sulfide ratio) when a large excess of oxygen is contained in the reaction mixture.

A resonance tunable and durable LSPR nano-particle sensor : AL2O3 capped silver nano-disks

Localized surface plasmon resonance (LSPR) biosensors are employed to detect target biomolecules which have particular resonance wavelengths. Accordingly, tunability of the LSPR wavelength is essential in designing LSPR devices. LSPR devices employing silver nano-particles present better efficiencies than those using other noble metals such as gold; however, silver nano-particles are easily oxidized when they come in contact with liquids, which is inevitable in biosensing applications. To attain both durability and tunabilty in a LSPR biosensor, this paper proposes alumina (AL₂O₃) capped silver nano-disks. It is shown that through controlling the thickness of the cap, the LSPR resonance frequency can be finely tuned over a wide range; and moreover, the cap protects silver nano-particles from oxidation and high temperature.