Cu and Fe oxides dispersed on SBA-15:a Fenton type bimetallic catalyst for N,N-diethyl-p-phenyl diamine degradation

A bimetallic oxidation catalyst has been synthesized via wet impregnation of copper and iron over a mesoporous SBA-15 silica support. Physicochemical properties of the resulting material were characterized by XRD, N2 physisorption, DRUVS, FTIR, Raman, SEM and HRTEM, revealing the structural integrity of the parent SBA-15, and presence of highly dispersed Cu and Fe species present as CuO and Fe2O3. The CuFe/SBA-15 bimetallic catalyst was subsequently utilized for the oxidative degradation of N,N-diethyl-p-phenyl diamine (DPD) employing a H2O2 oxidant in aqueous solution.

Selective oxidation of allylic alcohols over highly ordered Pd/meso-Al2 O3 catalysts

Highly ordered mesoporous alumina was prepared via evaporation induced self assembly and was impregnated to afford a family of Pd/meso-Al2O3 catalysts for the aerobic selective oxidation (selox) of allylic alcohols under mild reaction conditions. CO chemisorption and XPS identify the presence of highly dispersed (0.9–2 nm) nanoparticles comprising heavily oxidised PdO surfaces, evidencing a strong palladium-alumina interaction. Surface PdO is confirmed as the catalytically active phase responsible for allylic alcohol selox, with initial rates for Pd/meso-Al2O3 far exceeding those achievable for palladium over either amorphous alumina or mesoporous silica supports. Pd/meso-Al2O3 is exceptionally active for the atom efficient selox of diverse allylic alcohols, with activity inversely proportional to alcohol mass.

Operando synchronous DRIFTS/MS/XAS as a powerful tool for guiding the design of Pd catalysts for the selective oxidation of alcohols

The selective aerobic oxidation of crotyl alcohol to crotonaldehyde was investigated by time-resolved synchronous DRIFTS/MS/XAS over silica and alumina supported Pd nanoparticles. Alcohol and oxygen reactant feeds were cycled through the catalyst bed while dynamic measurements of the palladium oxidation state, molecular adsorbates and evolved product distribution were made simultaneously on a sub-second timescale. Highly dispersed palladium nanoparticles remained in a partially oxidised state

Support-enhanced selective aerobic alcohol oxidation over Pd/mesoporous silicas

The influence of silica mesostructure upon the Pd-catalyzed selective oxidation of allylic alcohols has been investigated for amorphous and surfactant-templated SBA-15, SBA-16, and KIT-6 silicas. Significant rate enhancements can be achieved via mesopore introduction, most notably through the use of interconnected porous silica frameworks, reflecting both improved mass transport and increased palladium dispersion; catalytic activity decreases in the order Pd/KIT-6 ≈ Pd/SBA-16 > Pd/SBA-15 > Pd/SiO2. Evidence is presented that highly dispersed palladium oxide nanoparticles, not zerovalent palladium, are the catalytically active species. © 2011 American Chemical Society.

Structural studies of high dispersion H3PW12O40/SiO2 solid acid catalysts

Highly dispersed H3PW12O40/SiO2 catalysts with loadings between 3.6 and 62.5 wt% have been synthesised and characterised. The formation of a chemically distinct interfacial HPW species is identified by XPS, attributed to pertubation of W atoms within the Keggin cage in direct contact with the SiO2 surface. EXAFS confirms the Keggin unit remains intact for all loadings, while NH3 adsorption calorimetery reveals the acid strength >0.14 monolayers of HPW is loading invariant with initial ΔHads = −164 kJ mol−1. Lower loading catalysts exhibit weaker acidity which is attributed to an inability of highly dispersed clusters to form crystalline water. For reactions involving non-polar hydrocarbons the interfacial species where the accessible tungstate is highest confer the greatest reactivity, while polar chemistry is favoured by higher loadings which can take advantage of the H3PW12O40 pseudo-liquid phase available within supported multilayers. © the Owner Societies 2006.

High activity, templated mesoporous SO4/ZrO2/HMS catalysts with controlled acid site density for α-pinene isomerisation

Highly active mesoporous SO4/ZrO2/HMS (hexagonal mesoroporous silica) solid acid catalysts with tuneable sulphated zirconia (SZ) content have been prepared for the liquid phase isomerisation of α-pinene. The mesoporous HMS framework is preserved during the grafting process as evidenced by the X-ray diffraction (XRD) and porosimetry with all SO4/ZrO2/HMS materials possessing average pore-diameters ∼20 Å. XRD confirms the presence of a stabilized tetragonal phase of nanoparticulate ZrO2, with no evidence for zirconia phase separation or the formation of discrete crystallites, consistent with a uniform and highly dispersed SZ coating. The activity towards α-pinene isomerisation scales linearly with Zr loading, while the specific activities are an order of magnitude greater than attainable by conventional methodologies (∼1 versus 0.08 mol h−1 g Zr−1).

Structure-reactivity correlations in the selective aerobic oxidation of cinnamyl alcohol:in situ XAFS

The structural evolution of a Pd/C catalyst during the liquid phase selective aerobic oxidation of cinnamyl alcohol has been followed by in situ XAFS and XPS. The fresh catalyst comprised highly dispersed, heavily oxidised Pd particles. Cinnamyl alcohol oxidation resulted in the rapid reduction of surface palladium oxide and a small degree of concomitant particle growth. These structural changes coincided with a large drop in catalytic activity. Prereduced Pd/C exhibited a significantly lower initial oxidation rate demonstrating the importance of surface metal oxide in effecting catalytic oxidation. Use of a Pd black model system confirmed that the oxide→metal transformation was the cause, and not result, of catalyst deactivation.

Photodeposition as a facile route to tunable Pt photocatalysts for hydrogen production:on the role of methanol

Photodeposition of H2PtCl6 in the presence of methanol promotes the formation of highly dispersed, metallic Pt nanoparticles over titania, likely via capture of photogenerated holes by the alcohol to produce an excess of surface electrons for substrate-mediated transfer to Pt complexes, resulting in a high density of surface nucleation sites for Pt reduction. Photocatalytic hydrogen production from water is proportional to the surface density of Pt metal co-catalyst, and hence photodeposition in the presence of high methanol concentrations affords a facile route to optimising photocatalyst design and highlights the importance of tuning co-catalyst properties in photocatalysis.

Optical fibre limits:an approach using ASE channel estimation

In this talk we investigate the usage of spectrally shaped amplified spontaneous emission (ASE) in order to emulate highly dispersed wavelength division multiplexed (WDM) signals in an optical transmission system. Such a technique offers various simplifications to large scale WDM experiments. Not only does it offer a reduction in transmitter complexity, removing the need for multiple source lasers, it potentially reduces the test and measurement complexity by requiring only the centre channel of a WDM system to be measured in order to estimate WDM worst case performance. The use of ASE as a test and measurement tool is well established in optical communication systems and several measurement techniques will be discussed [1, 2]. One of the most prevalent uses of ASE is in the measurement of receiver sensitivity where ASE is introduced in order to degrade the optical signal to noise ratio (OSNR) and measure the resulting bit error rate (BER) at the receiver. From an analytical point of view noise has been used to emulate system performance, the Gaussian Noise model is used as an estimate of highly dispersed signals and has had consider- able interest [3]. The work to be presented here extends the use of ASE by using it as a metric to emulate highly dispersed WDM signals and in the process reduce WDM transmitter complexity and receiver measurement time in a lab environment. Results thus far have indicated [2] that such a transmitter configuration is consistent with an AWGN model for transmission, with modulation format complexity and nonlinearities playing a key role in estimating the performance of systems utilising the ASE channel emulation technique. We conclude this work by investigating techniques capable of characterising the nonlinear and damage limits of optical fibres and the resultant information capacity limits. REFERENCES McCarthy, M. E., N. Mac Suibhne, S. T. Le, P. Harper, and A. D. Ellis, “High spectral efficiency transmission emulation for non-linear transmission performance estimation for high order modulation formats," 2014 European Conference on IEEE Optical Communication (ECOC), 2014. 2. Ellis, A., N. Mac Suibhne, F. Gunning, and S. Sygletos, “Expressions for the nonlinear trans- mission performance of multi-mode optical fiber," Opt. Express, Vol. 21, 22834{22846, 2013. Vacondio, F., O. Rival, C. Simonneau, E. Grellier, A. Bononi, L. Lorcy, J. Antona, and S. Bigo, “On nonlinear distortions of highly dispersive optical coherent systems," Opt. Express, Vol. 20, 1022-1032, 2012.

Support enhanced α-pinene isomerization over HPW/SBA-15

A family of mesoporous SBA-15 supported H3PW12O40 (HPW) catalysts were synthesized by wet-impregnation and compared with fumed silica analogues for the solventless isomerization of α-pinene under mild conditions. Structural and acidic properties of supported HPW materials were characterized by powder XRD, HRTEM, XPS, TGA, N2 porosimetry, DRIFTS, and ammonia and propylamine chemisorption and TPD. The high area, mesoporous SBA-15 architecture facilitates the formation of highly dispersed (isolated or low dimensional) HPW clusters and concomitant high acid site densities (up to 0.54 mmol g−1) relative to fumed silica wherein large HPW crystallites are formed even at low HPW loadings. α-Pinene exhibits a volcano dependence on HPW loading over the SBA-15 support due to competition between the number and accessibility of acid sites to the non-polar reactant, with the superior acid site accessibility for HPW/SBA-15 conferring a 10-fold rate enhancement with respect to HPW/fumed silica and pure HPW. Monocyclic limonene and terpinolene products are favoured over polycyclic camphene and β-pinene by weaker polyoxometallate analogues over SBA-15.

Highly selective hydrogenation of furfural over supported Pt nanoparticles under mild conditions

The selective liquid phase hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on SiO2, ZnO, γ-Al2O3, CeO2 is reported under extremely mild conditions. Ambient hydrogen pressure, and temperatures as low as 50 °C are shown sufficient to drive furfural hydrogenation with high conversion and >99% selectivity to furfuryl alcohol. Strong support and solvent dependencies are observed, with methanol and n-butanol proving excellent solvents for promoting high furfuryl alcohol yields over uniformly dispersed 4 nm Pt nanoparticles over MgO, CeO2 and γ-Al2O3. In contrast, non-polar solvents conferred poor furfural conversion, while ethanol favored acetal by-product formation. Furfural selective hydrogenation can be tuned through controlling the oxide support, reaction solvent and temperature.