Pulse-response TAP studies of the reverse water-gas shift reaction over a Pt/CeO2 catalyst

The temporal analysis of products (TAP) technique was successfully applied for the first time to investigate the reverse water-gas shift (RWGS) reaction over a 2% Pt/CeO2 catalyst. The adsorption/desorption rate constants for CO2 and H-2 were determined in separate TAP pulse-response experiments, and the number of H-containing exchangeable species was determined using D-2 multipulse TAP experiments. This number is similar to the amount of active sites observed in previous SSITKA experiments. The CO production in the RWGS reaction was studied in a TAP experiment using separate (sequential) and simultaneous pulsing Of CO2 and H-2. A small yield of CO was observed when CO2 was pulsed alone over the reduced catalyst, whereas a much higher CO yield was observed when CO2 and H-2 were pulsed consecutively. The maximum CO yield was observed when the CO2 pulse was followed by a H-2 pulse with only a short (1 s) delay. Based on these findings, we conclude that an associative reaction mechanism dominates the RWGS reaction under these experimental conditions. The rate constants for several elementary steps can be determined from the TAP data. In addition, using a difference in the time scale of the separate reaction steps identified in the TAP experiments, it is possible to distinguish a number of possible reaction pathways. (c) 2005 Elsevier Inc. All rights reserved.

Expansion of pulse responses from temporal analysis of products (TAP) pulse responses for more accurate data analysis

TAP pulse responses are normally analysed using moments, which are integrals of the full TAP pulse response. However, in some cases the entire pulse response may not be recorded due to technical reasons, thereby compromising any data analysis due to moments generated from incomplete pulse responses. The current work discloses the development of a function which mathematically expands the tail of a TAP pulse response, so that the TAP data analysis can be accurately conducted. This newly developed analysis method has been applied to the oxidative dehydrogenation of ethane over Co–Cr–Sn–WOx/α-Al2O3 and Co–Cr–Sn–WOx/α-Al2O3 catalysts as a case study.

TAP Reactor Development and Application in the Kinetic Characterization of Catalysts for Heterogeneously Catalyzed Gas Phase Reactions

This manuscript describes the application and further development of the TAP technique in kinetic characterization of heterogeneous catalysis. The major application of TAP systems is to study mechanisms, kinetics and transport phenomena in heterogeneous catalysis, all of which is made possible by the sub-millisecond time resolution. Furthermore, the kinetic information obtained can be used to gain an insight into the mechanism occurring over the catalyst system. This is advantageous as heterogeneous catalysts with an improved efficiency can be developed as a result. TAP kinetic studies are carried out at low pressure (~1x10-7 mbar) and TAP pulses are sufficiently small (1013-1015 molecules) so as to maintain this low pressure. The use of a small number of molecules in comparison to the total number of active sites means the state of the catalyst remains relatively unchanged. The use of the low intensity pulses also makes the pressure gradient negligible and so allows the TAP reactor system to operate in the Knudsen Diffusion regime, where gas-gas reactions are eliminated. Hence only gas-catalyst reactions are investigated and, by the use of moment analysis of observed exit flow, rate constants of elementary steps of the reaction can be obtained.

In this manuscript, two attempts to further the TAP technique are reported. Firstly, the work undertaken at QUB to attempt to control the number of molecules of condensable reagents that can be pulsed during a TAP pulse experiment is disclosed. Secondly, a collaborative project with SAI Ltd Manchester is discussed in a separate chapter, where technical details and validation of a customised time of flight mass spectrometer (ToF MS) for the QUB TAP-1 system are reported. A collaborative project with Cardiff Catalysis Institute focusing on the study of CO oxidation over hopcalite catalysts is also reported. The analysis of the experimental results has provided an insight into the possible mechanism of the oxidation of CO over these catalysts. A correction function has also been derived which accounts for the adsorption of reactant molecules over inert materials that are used for the reactor packing in TAP experiments. This function was then applied to the selective reduction of O2 in a H2 rich ethene feed, so that more accurate TAP moment based analysis could be conducted.

Full-Wave Analysis of Layered Aperture Arrays

The new rigorous numerical-analytical technique based upon Galerkin method with the entire domain basis functions has been developed and applied to the study of the periodic aperture arrays containing multiple dissimilar apertures of complex shapes in stratified medium. The rapid uniform convergence of the solutions has enabled a comprehensive parametric study of complex array arrangements. The developed theory has revealed new effects of the aperture shape and layout on the array performance. The physical mechanisms underlying the TM wave resonances and Luebbers' anomaly have been explained for the first time.

Spatial Demultiplexing in the sub-millimeter wave band using multlayer free-standing frequency selective surfaces

In this paper, we show that a multilayer freestanding slot array can be designed to give an insertion loss which is significantly lower than the value obtainable from a conventional dielectric backed printed frequency selective surface (FSS). This increase in filter efficiency is highlighted by comparing the performance of two structures designed to provide frequency selective beamsplitting in the quasioptical feed train of a submillimeter wave space borne radiometer. A two layer substrateless FSS providing more than 20 dB of isolation between the bands 316.5â??325.5 GHz and 349.5â??358.5 GHz, gives an insertion loss of 0.6 dB when the filter is orientated at 45 incidence in the TM plane, whereas the loss exhibited by a conventional printed FSS is in excess of 2 dB. A similar frequency response can be obtained in the TE plane, but here a triple screen structure is required and the conductor loss is shown to be comparable to the absorption loss of a dielectric backed FSS. Experimental devices have been fabricated using a precision micromachining technique. Transmission measurements performed in the range 250â??360 GHz are in good agreement with the simulated spectral performance of the individual periodic screens and the two multilayer freestanding FSS structures.

Quadrifilar Loop Antenna

A new quadrifilar antenna has been developed for generating circularly polarized backfire radiation. The antenna consists of two orthogonal rectangular conducting loops, each incorporating capacitive coupling and fed using either a single or two coaxial cables. Though the geometry is much simpler than a conventional quadrifilar helix antenna, the radiation pattern performance is very similar. Measured and simulated patterns are compared for two antennas with different feed arrangements. It is shown that the resonant structure can produce a cardioid pattern with a directivity of 4.5 dB (120 3-dB beamwidth) and a front-to-back ratio of more than 20 dB at the center operating frequency. A 10% impedance bandwidth (VSWR

Mechanically tunable multiband compact quadrifilar helix antenna with dual mode operation

We show that by introducing a gap at the center of the helical sections (where the current is minimum) of a lambda/2 quadrifilar helix antenna (QHA) and varying the axial length and radial gap between the overlapping volutes, the antenna gives a 28% impedance bandwidth which is nine times the bandwidth of a conventional QHA. A 16% bandwidth with a front to back ratio of >= 14 dB is achievable with 5-14% reduction in the size of the QHA. The structure can yield a monopole radiation pattern suitable for terrestrial applications or a hemispherical pattern suitable for satellite use. The simulation results are validated by measurements at L-band.

Single feed low profile omnidirectional antenna with slant 45 degrees linear polarization

It is shown that a side-fed bifilar helix antenna with a single feed, can generate a slant 451 linearly polarized onmidirectional toroidal pattern. The antenna has a low profile and does not require a ground plane. The bifilar helix antenna provides slant 45 degrees polarization over a solid angle of almost 4 pi steradians as compared to a crossed dipole which generates a tilted 45 degrees linearly, polarized pattern only over a solid angle of 1.14 pi steradians. The computed results are validated by experimental data.

A surface plasmon resonance biosensor assay for the simultaneous determination of thiamphenicol, florefenicol, florefenicol amine and chloramphenicol residues in shrimps

A rapid and sensitive screening qualitative method using a surface plasmon resonance (SPR) biosensor was developed which can detect of all fenicol antibiotic residues in shrimps from a single sample extract. This method requires ethyl acetate extraction followed by a single wash with isooctane/chlorofonrm. Each sample extract is injected over the surfaces of two biosensor chip flow cells, one surface having the capability to detect florefenicol amine (FF amine), florefenicol (FF), and thiamphenicol (TAP) and the second surface for chloramphenicol (CAP) detection. The estimated detection capabilities (CC beta) were 0. 1, 0.2, 250, and 0.5 ppb for CAP, FF, FF amine, and TAP, respectively. This quick, simple test allowed the detection of CAP residues in shrimps at the minimum required performance limit (MRPL) of 0.1 mu g kg(-1) for this compound and of FF, FF amine, and TAP below their maximum residue limits (MRLs). (c) 2006 Elsevier B.V. All rights reserved.

Characterisation of antibodies to chloramphenicol, produced in different species by enzyme-linked immunosorbent assay and biosensor technologies

Six polyclonal antisera to chloramphenicol (CAP) were successfully raised in camels, donkeys and goats. As a comparison of sensitivity, IC50 values ranged from 0.3 ng mL(-1) to 5.5 ng mL(-1) by enzyme-linked immunosorbent assay (ELISA) and from 0.7 ng mL(-1) to 1.7 ng mL(-1) by biosensor assay. The introduction of bovine milk extract improved the sensitivity of four of the antisera by ELISA and two by biosensor assay; a reduction in sensitivity of the remaining antisera ranged by a factor of 1.1-2.6. Porcine kidney extract reduced the sensitivity of all the antisera by a factor ranging from 1.1 to 7 by ELISA and a factor of 1.5 to 4 by biosensor. A low cross-reactivity with thiamphenicol (TAP) and florfenicol (FF) was displayed by antiserurn G2 (1.2% and 18%, respectively) when a homologous ELISA assay format was employed. No cross-reactivity was displayed by any of the antisera when a homologous biosensor assay format was employed. Switching to a heterologous ELISA format prompted three of the antisera to display more significant cross-reactivity with TAP and FF (53% and 82%, respectively, using Dl). The heterologous biosensor assay also increased the cross-reactivity of D1 for TAP and FF (56% and 129%, respectively) and of one other antiserum (Gl) to a lesser degree. However, unlike the ELISA, the heterologous biosensor assay produced a substantial reduction in sensitivity (by a factor of 6 for D1). (C) 2007 Elsevier B.V. All rights reserved.

Effect of the carburization of MoO3-based catalysts on the activity for butane hydroisomerization

Catalysts based on molybdena (MoO3) reduced at mild temperatures are highly active and selective for the hydroisomerization of alkanes: however, further catalyst development has been hampered by the structural complexity of the material and the controversy regarding the nature of the active phase. The present work is aimed at determining the relationship between the content of carbon present in an oxycarbide phase and the activity for n-butane hydroisomerization. A series of temperature-programmed oxidation (TPO) and temporal analysis of product (TAP) data showed that the oxycarbidic carbon content is not related to the activity of the sample for the isomerization of n-butane to isobutane. The formation of a carbon-containing phase is, therefore, not crucial to obtain an active catalyst. This study also highlights the capability of the multi-pulse TAP technique to investigate structure-activity relationships over materials with readily variable atomic composition. (C) 2008 Elsevier B.V. All rights reserved.

The investigation of mechanisms in environmental catalysis using time-resolved methods

The formation of nitrogen oxides (NOx) during a combustion process is difficult to avoid because of the large exotherm and the consequent problem of avoiding local high-temperature spikes. Consequently, for many applications, such as for automotive power generation, there will be a continuing need to use catalytic after-treatment to reduce harmful emissions. The investigation of the mechanisms of the key catalytic reactions in environmental catalysis can provide an insight into the action of the catalyst, and time-resolved methods offer a powerful means to study these processes under realistic conditions. The use of Temporal Analysis of Products (TAP) and Steady State Isotopic Transient Kinetic Analysis (SSITKA) methods to investigate the reduction of NOx under various experimental conditions is described. From a detailed analysis of the SSITKA profiles, it is shown that at low temperatures the mechanism for the formation of N-2 and N2O from NO may differ from the conventional high-temperature mechanism. This is supported by density functional theory calculations, which show that the barrier to the formation of N2O from the reaction of N(ads) and NO(ads) may be too high to allow this process to occur at low temperatures. The alternative reaction of NO(ads) + NO(ads) = N2O(g) + O(ads) is shown to be much more favorable and is consistent with the SSITKA analysis. The remarkable effect of hydrogen as a reductant at low temperatures is described, and alternative interpretations of the role of hydrogen are discussed.

Submillimeter wave frequency selective surface with polarisation independent spectral responses

This paper reports the design, construction and electromagnetic performance of a new freestanding frequency selective surface (FSS) structure which generates coincident spectral responses for dual polarisation excitation at oblique angles of incidence. The FSS is required to allow transmission of 316.5 - 325.5 GHz radiation with a loss = 0.6 dB and to achieve = 30 dB rejection from 349.5 - 358.5 GHz. It should also exhibit crosspolarisation levels below -25 dB, all criteria being satisfied simultaneously for TE and TM polarisations at 45° incidence. The filter consists of two identical, 30 mm diameter, 12.5 ?m thick, optically flat, perforated metal screens separated by 450 ?m. Each of the ˜5000 unit cells contains two nested, short circuited, rectangular loop slots and a rectangular dipole slot. The nested elements provide a passband spectral response centred at 320 GHz in the TE and TM planes; the dipole slot increases the filter roll-off above resonance. The FSS was fabricated from silicon-on-insulator wafers using precision micromachining and plating processes including the use of Deep Reactive Ion Etching (DRIE) to pattern the individual slots and remove the substrate under the periodic arrays. Quasi–optical transmission measurements in the 250 – 360 GHz range yielded virtually identical copolarised spectral responses, with the performance meeting or exceeding the above specifications. Experimental results are in excellent agreement with numerical predictions.

Design and measurement of reconfigurable millileter wave reflectarray cells with nematic liquid crystal

Numerical simulations are used to study the electromagnetic scattering from phase agile microstrip reflectarray cells which exploit the voltage controlled dielectric anisotropy property of nematic state liquid crystals (LC). In the computer model two arrays of equal size elements constructed on a 15?m thick tuneable LC layer were designed to operate at centre frequencies of 102 GHz and 130 GHz. Micromachining processes based on the metallization of quartz/silicon wafers and an industry compatible LCD packaging technique were employed to fabricate the grounded periodic structures. The loss and phase of the reflected signals were measured using a quasi-optical test bench with the reflectarray cells inserted at the beam waist of the imaged Gaussian beam, thus eliminating some of the major problems associated with traditional free-space characterisation at these frequencies. By applying a low frequency AC bias voltage of 10 V, a 165o phase shift with a loss 4.5 dB-6.4 dB at 102 GHz and 130o phase shift with a loss variation between 4.3 dB – 7 dB at 130 GHz was obtained. The experimental results are shown to be in close agreement with the computer model.

Simple and accurate analytical model of planar grids and high-impedance surfaces, comprising metal strips or patches

Simple analytical formulas are introduced for the grid impedance of electrically dense arrays of square patches and for the surface impedance of high-impedance surfaces based on the dense arrays of metal strips or square patches over ground planes. Emphasis is on the oblique-incidence excitation. The approach is based on the known analytical models for strip grids combined with the approximate Babinet principle for planar grids located at a dielectric interface. Analytical expressions for the surface impedance and reflection coefficient resulting from our analysis are thoroughly verified by full-wave simulations and compared with available data in open literature for particular cases. The results can be used in the design of various antennas and microwave or millimeter wave devices which use artificial impedance surfaces and artificial magnetic conductors (reflect-array antennas, tunable phase shifters, etc.), as well as for the derivation of accurate higher-order impedance boundary conditions for artificial (high-) impedance surfaces. As an example, the propagation properties of surface waves along the high-impedance surfaces are studied.