A glimpse of the inner workings of the templated site.

This is the first direct experimental probe, using EXAFS, of the active site within molecularly imprinted polymers and paves the way to a more detailed understanding of the inner workings of molecular imprinting.

Optically detected X-ray absorption spectroscopy measurements as a means of monitoring corrosion layers on copper.

XANES and EXAFS information is conventionally measured in transmission through the energy-dependent absorption of X-rays or by observing X-ray fluorescence, but secondary fluorescence processes, such as the emission of electrons and optical photons (e.g., 200-1000 nm), can also be used as a carrier of the XAS signatures, providing complementary information such as improved surface specificity.

Structure-performance relationships of Rh and RhPd alloy supported catalysts using combined EDE/DRIFTS/MS.

Energy dispersive extended X-ray absorption fine structure spectroscopy (ED-XAFS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and mass spectrometry (MS), have been combined for the structure-function study of Rh and RhPd supported catalysts for the reduction of NO by CO. The combined results show that although alloying of Rh with Pd prevents the dissociative oxidation of the Rh by NO, it does not prevent the extensive disruptive oxidation of Rh by CO. The influence of oxidative disruption by molecular CO in such systems may therefore be far more pervasive and catalytically important than has been previously observed.

Access to well-defined isolated Fe(II) centers on silica and their use in oxidation.

Well-defined Fe(II) isolated sites are obtained by reaction of diaryl-N,N'-diazadiene bis(neosilyl) iron (1) with an aerosil silica, SiO(2-(700)). This system can be used as a precursor for the catalytic oxidation of cyclohexene into cyclohexene oxide, cyclohexenol and cyclohexenone in the presence of H(2)O(2).

Probing key coordination interactions: configurationally restricted metal activated CXCR4 antagonists.

The syntheses of configurationally restricted mono- and bis-macrocyclic copper(II) perchlorate complexes (copper(II) 5-benzyl-1,5,8,12-tetraazabicyclo[10.2.2]hexadecane and dicopper(II) 5,5'-[1,4-phenylenebis(methylene)]-bis(1,5,8,12-tetraazabicyclo[10.

Comparative experimental and EXAFS studies in the Mizoroki-Heck reaction with heteroatom-functionalised N-heterocyclic carbene palladium catalysts.

A study on the Mizoroki-Heck coupling of selected aryl bromides with acrylates catalysed by a series of Pd complexes of bidentate pyridyl-, picolyl-, diphenylphosphinoethyl- and diphenylphosphinomethyl-functionalised N-heterocyclic carbene (NHC) is reported. The observed activity is dependent on the type of solvent and base used and the nature of the "classical" donors of the mixed-donor bidentate ligand and its bite angle. A mechanistic model is presented for the pyridine-functionalised NHC complexes based on an in situ EXAFS study under dilute catalyst conditions (2 mM Pd).

Well-defined surface imido amido tantalum(v) species from ammonia and silica-supported tantalum hydrides.

The MCM-41 supported hydrides [([triple bond]SiO)(2)TaH(3)], 1a, and [([triple bond]SiO)(2)TaH(3)], 1b, cleave N-H bonds of ammonia at room temperature to yield the well-defined imido amido surface complexes [([triple bond]SiO)(2)Ta(NH)(NH(2))], 2, and 2xNH(3). Additionally, the surface silanes [[triple bond]Si-H] that exist in close proximity to 1a and 1b also react with ammonia at room temperature to give the surface silylamido [Si-NH(2)]. Such reaction is tantalum assisted: surface silanes were synthesized independently and in absence of tantalum by reaction of highly strained silica, SiO(2-1000), with SiH(4) and no reaction with ammonia was observed.

Identification of the surface species responsible for N2O formation from the chemisorption of NO on Rh/alumina.

Energy dispersive EXAFS (EDE) and diffuse reflectance infrared spectroscopy (DRIFTS) are combined synchronously at high time resolution (17 Hz) to probe how NO(g) reacts with gamma-Al(2)O(3) supported, metallic Rh nanoparticles of an average 11 A diameter; a bent nitrosyl species is considered to be the key to the formation of N(2)O.

Selective oxidation of benzene to phenol over FeAlPO catalysts using nitrous oxide as oxidant.

A tetrahedrally coordinated iron in framework substituted microporous AlPO-5 catalysts are shown to be active and selective for the hydroxylation of benzene to phenol, using nitrous oxide as the oxidant.

Rapid monitoring of the nature and interconversion of supported catalyst phases and of their influence upon performance: CO oxidation to CO2 by gamma-Al2O3 supported Rh catalysts.

Spatially and temporally resolved energy-dispersive EXAFS (EDE) has been utilised in situ to study supported Rh nanoparticles during CO oxidation by O2 under plug-flow conditions. Three distinct phases of Rh supported upon Al2O3 were identified by using EDE at the Rh K-edge during CO oxidation. Their presence and interconversion are related to the efficiency of the catalysts in oxidising CO to CO2.

Oxidation/reduction kinetics of supported Rh/Rh2O3 nanoparticles in plug flow conditions using dispersive EXAFS.

The kinetics of oxidation and reduction of Al(2)O(3) supported Rh nanoparticles have been determined on a 50 millisecond timescale using energy dispersive EXAFS (EDE).

Synchronous, time resolved, diffuse reflectance FT-IR, energy dispersive EXAFS (EDE) and mass spectrometric investigation of the behaviour of Rh catalysts during NO reduction by CO.

Synchronous, time resolved, infra-red, XAFS, and mass spectroscopies are simultaneously applied in situ to the investigation of the dynamic behaviour of Rh/Al2O3 catalysts during NO reduction by CO; NO conversion, and its kinetic character are closely correlated to the conversion of Rh(I)(predominantly RhI(CO)2) to Rh(0).

Extended X-ray absorption fine structure (EXAFS) characterisation of the hydroformylation of oct-1-ene by dilute Rh-PEt3 catalysts in supercritical carbon dioxide.

Dilute EXAFS characterisation has been used to elucidate species involved during the course of the 3 mM Rh-catalysed hydroformylation of oct-1-ene in scCO(2); significant metal clustering occurs with a Rh:P ratio of 1:1 but at a 1:3 ratio, metal clustering is not detected, with the presence of monomer species only.

Extended X-ray absorption fine structure (EXAFS) characterisation of dilute palladium homogeneous catalysts.

Highly dilute EXAFS characterisation for the elucidation of species involved in Heck chemistry is demonstrated; the major "monomer" species of Herrmann's acetate-bridged phosphapalladadacycle is characterised and species present during the course of a 50 ppm [Pd] Pd(OAc)2/PBu(t)3 catalysed Heck reaction are presented.

Contrasting dynamic responses of supported Rh nanoparticles to H2S and SO2 and subsequent poisoning of NO reduction by H2.

H2S induces rapid sulfidation of the Rh nanoparticles at room temperature and completely poisons NO reduction by H2; SO2 elicits an equally rapid but subtle modification of nanoparticle structure but has little effect upon NO reduction at 523 K.

Susceptibility of a heterogeneous catalyst, Rh/gamma-alumina, to rapid structural change by exposure to NO.

Metal particles in a Rh/gamma-Al2O3 catalyst of differing particle size are oxidised by NO/He within 5 seconds at 313 K; rapid, highly exothermic dissociative chemisorption of NO is the initial step.