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.

Experimental transmission of dispersion managed solitons

This thesis investigates the feasibility of soliton transmission at 1150nm over standard fibre. This is done using a dispersion compensating fibre module in each amplifier span to compensate for the high dispersion. The basic principles of soliton propagation in optical fibre are discussed within this thesis, followed by an introduction to advantages of dispersion management. In the experimental chapter single channel transmission results are presented in 10Gbit/s and 40Gbit/s. At 10Gbit/s the effects of dispersion management on the power dispersion relationship for solitons are investigated. The detrimental effects of soliton-soliton interactions, which are increased due to the greater overlap breathing solitons are discussed. A technique for reducing the soliton-soliton interactions through amplifier positioning is presented as a solution to this problem. The experiments demonstrate the feasibility of using standard fibre for transmission over trans-oceanic distances at 10Gbit/s. The 40Gbit/s experiment demonstrates transmission over sufficient distance for an terrestrial system. Also contained within this thesis are experimental results showing transmission of solitons over dispersion shifted fibre using a novel technique that makes use of the non-linear polarisation rotation of the soliton in the fibre. This is used to generate the effect of saturable absorption, allowing transmission distances of 200,000km to be achieved.

Alumina-grafted SBA-15 as a high performance support for Pd-catalysed cinnamyl alcohol selective oxidation

Ultrathin alumina monolayers grafted onto an ordered mesoporous SBA-15 silica framework afford a composite catalyst support with unique structural properties and surface chemistry. Palladium nanoparticles deposited onto Al-SBA-15 via wet impregnation exhibit the high dispersion and surface oxidation characteristic of pure aluminas, in conjunction with the high active site densities characteristic of thermally stable, high-area mesoporous silicas. This combination confers significant rate enhancements in the aerobic selective oxidation (selox) of cinnamyl alcohol over Pd/Al-SBA-15 compared to mesoporous alumina or silica supports. Operando, liquid-phase XAS highlights the interplay between dissolved oxygen and the oxidation state of palladium nanoparticles dispersed over Al-SBA-15 towards on-stream reduction: ambient pressures of flowing oxygen are sufficient to hinder palladium oxide reduction to metal, enabling a high selox activity to be maintained, whereas rapid PdO reduction and concomitant catalyst deactivation occurs under static oxygen. Selectivity to the desired cinnamaldehyde product mirrors these trends in activity, with flowing oxygen minimising CO cleavage of the cinnamyl alcohol reactant to trans-β-methylstyrene, and of cinnamaldehyde decarbonylation to styrene. © 2013 Elsevier B.V.

Optimising transmission capacity: long distance and terrestrial applications

This paper identifies the important limiting processes in transmission capacity for amplified soliton systems. Some novel control techniques are described for optimizing this capacity. In particular, dispersion compensation and phase conjugation are identified as offering good control of jitter without the need for many new components in the system. An advanced average soliton model is described and demonstrated to permit large amplifier spacing. The potential for solitons in high-dispersion land-based systems is discussed and results are presented showing 10 Gbit s$^{-1}$ transmission over 1000 km with significant amplifier spacing.

Digital back-propagation for spectrally efficient WDM 112 Gbit/s PM m-ary QAM transmission

We report the performance of coherently-detected nine-channel WDM transmission over high dispersion fibers, using polarization multiplexed m-ary quadrature amplitude modulation (m = 4, 16, 64, 256) at 112 Gbit/s. Compensation of fiber nonlinearities via digital back-propagation enables up to 10 dB improvement in maximum transmittable power and similar to 8 dB Q(eff) improvement which translates to a nine-fold enhancement in transmission reach for PM-256QAM, where the largest improvements are associated with higher-order modulation formats. We further demonstrate that even under strong nonlinear distortion the transmission reach only reduces by a factor of similar to 2.5 for a 2 unit increase in capacity (log(2)m) when full band DBP is employed, in proportion to the required back-to-back OSNR.

Optimising transmission capacity: long distance and terrestrial applications

This paper identifies the important limiting processes in transmission capacity for amplified soliton systems. Some novel control techniques are described for optimizing this capacity. In particular, dispersion compensation and phase conjugation are identified as offering good control of jitter without the need for many new components in the system. An advanced average soliton model is described and demonstrated to permit large amplifier spacing. The potential for solitons in high-dispersion land-based systems is discussed and results are presented showing 10 Gbit s$^{-1}$ transmission over 1000 km with significant amplifier spacing.

NLSE-based model of a random distributed feedback fiber laser

In this work we propose a NLSE-based model of power and spectral properties of the random distributed feedback (DFB) fiber laser. The model is based on coupled set of non-linear Schrödinger equations for pump and Stokes waves with the distributed feedback due to Rayleigh scattering. The model considers random backscattering via its average strength, i.e. we assume that the feedback is incoherent. In addition, this allows us to speed up simulations sufficiently (up to several orders of magnitude). We found that the model of the incoherent feedback predicts the smooth and narrow (comparing with the gain spectral profile) generation spectrum in the random DFB fiber laser. The model allows one to optimize the random laser generation spectrum width varying the dispersion and nonlinearity values: we found, that the high dispersion and low nonlinearity results in narrower spectrum that could be interpreted as four-wave mixing between different spectral components in the quasi-mode-less spectrum of the random laser under study could play an important role in the spectrum formation. Note that the physical mechanism of the random DFB fiber laser formation and broadening is not identified yet. We investigate temporal and statistical properties of the random DFB fiber laser dynamics. Interestingly, we found that the intensity statistics is not Gaussian. The intensity auto-correlation function also reveals that correlations do exist. The possibility to optimize the system parameters to enhance the observed intrinsic spectral correlations to further potentially achieved pulsed (mode-locked) operation of the mode-less random distributed feedback fiber laser is discussed.

Influence of alkyl chain length on sulfated zirconia catalysed batch and continuous esterification of carboxylic acids by light alcohols

The impact of alkyl chain length on the esterification of C2–C16 organic acids with C1–C4 alcohols has been systematically investigated over bulk and SBA-15 supported sulfated zirconias (SZs). Rates of catalytic esterification for methanol with acetic acid are directly proportional to the sulfur content for both SZ and SZ/SBA-15, with the high dispersion of SZ achievable in conformal coatings over mesoporous SBA-15 confering significant rate-enhancements. Esterification over the most active 0.24 mmol gcat−1 bulk SZ and 0.29 mmol gcat−1 SZ/SBA-15 materials was inversely proportional to the alkyl chain length of alcohol and acid reactants; being most sensitive to changes from methanol to ethanol and acetic to hexanoic acids respectively. Kinetic analyses reveal that these alkyl chain dependencies are in excellent accord with the Taft relationship for polar and steric effects in aliphatic systems and the enthalpy of alcohol adsorption, implicating a Langmuir–Hinshelwood mechanism. The first continuous production of methyl propionate over a SZ fixed-bed is also demonstrated.

Polarisation mode dispersion induced transmission penalties for long-haul high speed optical communication systems

Results of full numerical simulations of a guiding-centre soliton system with randomly birefringent SMF fibre are shown and analysed. It emerges that the soliton system becomes unstable even for small amounts of PMD.

Dispersion-managed solitons: a new paradigm for high data rate

The WDM properties of dispersion managed (DM) solitons and the reduction in Gordon-Haus jitter means that it is possible to contemplate multiple channels each at 10 Gbit/s for transoceanic distances without the need for elaborate soliton control. This paper will concentrate on fundamental principles of DM solitons, but will use these principles to indicate optimum maps for future high-speed soliton systems.

Ultra high-speed transmission using dispersion managed solitons

This thesis presents the results of numerical modelling of ultra high-speed transmission using DM solitons. The theory of propagation in optical fibres is presented with specific reference to optical communication systems. This theory is then expanded to. incorporate dispersion-managed transmission and the dispersion managed soliton. The first part of this work focuses on ultra high-speed dispersion managed soliton propagation in short period dispersion maps. Initially, the cbaracteristics .of dispersion managed soliton propagation in short period dispersion maps are contrasted to those of the more conventional dispersion managed regime. These properties are then utilised to investigate transmission at single channel data rates of 80 Gbit/s, 160 Gbit/s and 320 Gbit/s. For all three data rates, the tolerable limits for transmission over 1000 km, 3000 km and·transoceanic distances are defined. A major limitation of these higher bjt rate systems arises from the problem of noise-induced interactions, which is where the.accumulation of timing jitter causes neighbouring dispersion-managed solitons to interact. In addition, the systems become more sensitive to initial conditions as the data rate increases, .. The second part of the work focuses on contrasting the performance of a range of propagation regimes, from quasi-linear through to soliton-like propagation at 40 Gbit/s for both single channel and WDM dispersion managed transmission. The results indicated that whilst the optimal single channel performance was achieved for soliton-like propagation, the optimal WDM performance was achieved for propagation regime that lay between quasi-linear and soliton-like.