18 resultados para Time-resolved spectroscopy

em Aston University Research Archive


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We investigate the use of different direct detection modulation formats in a wavelength switched optical network. We find the minimum time it takes a tunable sampled grating distributed Bragg reflector laser to recover after switching from one wavelength channel to another for different modulation formats. The recovery time is investigated utilizing a field programmable gate array which operates as a time resolved bit error rate detector. The detector offers 93 ps resolution operating at 10.7 Gb/s and allows for all the data received to contribute to the measurement, allowing low bit error rates to be measured at high speed. The recovery times for 10.7 Gb/s non-return-to-zero on–off keyed modulation, 10.7 Gb/s differentially phase shift keyed signal and 21.4 Gb/s differentially quadrature phase shift keyed formats can be as low as 4 ns, 7 ns and 40 ns, respectively. The time resolved phase noise associated with laser settling is simultaneously measured for 21.4 Gb/s differentially quadrature phase shift keyed data and it shows that the phase noise coupled with frequency error is the primary limitation on transmitting immediately after a laser switching event.

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An experimental method for characterizing the time-resolved phase noise of a fast switching tunable laser is discussed. The method experimentally determines a complementary cumulative distribution function of the laser's differential phase as a function of time after a switching event. A time resolved bit error rate of differential quadrature phase shift keying formatted data, calculated using the phase noise measurements, was fitted to an experimental time-resolved bit error rate measurement using a field programmable gate array, finding a good agreement between the time-resolved bit error rates.

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We demonstrate a novel time-resolved Q-factor measurement technique and demonstrate its application in the analysis of optical packet switching systems with high information spectral density. For the first time, we report the time-resolved Q-factor measurement of 42.6 Gbit/s AM-PSK and DQPSK modulated packets, which were generated by a SGDBR laser under wavelength switching. The time dependent degradation of Q-factor performance during the switching transient was analyzed and was found to be correlated with different laser switching characteristics in each case.

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We investigate the use of different direct detection modulation formats in a wavelength switched optical network. We find the minimum time it takes a tunable sampled grating distributed Bragg reflector laser to recover after switching from one wavelength channel to another for different modulation formats. The recovery time is investigated utilizing a field programmable gate array which operates as a time resolved bit error rate detector. The detector offers 93 ps resolution operating at 10.7 Gb/s and allows for all the data received to contribute to the measurement, allowing low bit error rates to be measured at high speed. The recovery times for 10.7 Gb/s non-return-to-zero on–off keyed modulation, 10.7 Gb/s differentially phase shift keyed signal and 21.4 Gb/s differentially quadrature phase shift keyed formats can be as low as 4 ns, 7 ns and 40 ns, respectively. The time resolved phase noise associated with laser settling is simultaneously measured for 21.4 Gb/s differentially quadrature phase shift keyed data and it shows that the phase noise coupled with frequency error is the primary limitation on transmitting immediately after a laser switching event.

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X-ray photoelectron spectroscopy (XPS) can play an important role in guiding the design of new materials, tailored to meet increasingly stringent constraints on performance devices, by providing insight into their surface compositions and the fundamental interactions between the surfaces and the environment. This chapter outlines the principles and application of XPS as a versatile, chemically specific analytical tool in determining the electronic structures and (usually surface) compositions of constituent elements within diverse functional materials. Advances in detector electronics have opened the way for development of photoelectron microscopes and instruments with XPS imaging capabilities. Advances in surface science instrumentation to enable time-resolved spectroscopic measurements offer exciting opportunities to quantitatively investigate the composition, structure and dynamics of working catalyst surfaces. Attempts to study the effects of material processing in realistic environments currently involves the use of high- or ambient-pressure XPS in which samples can be exposed to reactive environments.

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The selective oxidation of crotyl alcohol to crotonaldehyde over ultrathin Au overlayers on Pd(1 1 1) and Au/Pd(1 1 1) surface alloys has been investigated by time-resolved X-ray photoelectron spectroscopy (XPS) and mass spectrometry. Pure gold is catalytically inert towards crotyl alcohol which undergoes reversible adsorption. In contrast, thermal processing of a 3.9 monolayer (ML) gold overlayer allows access to a range of AuPd surface alloy compositions, which are extremely selective towards crotonaldehyde production, and greatly reduce the extent of hydrocarbon decomposition and eventual carbon laydown compared with base Pd(1 1 1). XPS and CO titrations suggest that palladium-rich surface alloys offer the optimal balance between alcohol oxidative dehydrogenation activity while minimising competitive decomposition pathways, and that Pd monomers are not the active surface ensemble for such selox chemistry over AuPd alloys. Crown Copyright © 2008.

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Here we demonstrate the first application of time-resolved synchrotron X-ray absorption spectroscopy to simultaneously follow dynamic nanoparticle surface restructuring and the evolution of surface and gas-phase products during an organic reaction. Surface palladium oxide, and not metal, is identified as the catalytic species responsible for the selective oxidation (selox) of crotyl alcohol to crotonaldehyde. Elevated reaction temperatures facilitate reversible nanoparticle redox processes, and concomitant catalytic selectivity loss, in response to reaction conditions. These discoveries highlight the importance of stabilizing surface palladium oxide and minimizing catalyst reducibility in order to achieve high selox yields, and will aid the future design of Pd-derived selox catalysts. This discovery has important implications for the design of future liquid and vapor phase selox catalysts, and the thermochemical behavior of Pd nanostructures in general.

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An ordered macroporous host (mac-SiO2) has been used to prevent aggregation of layered photocatalysts based on carbon nitride. Using typical carbon nitride synthesis conditions, cyanamide was condensed at 550 °C in the presence and absence of mac-SiO2. Condensation in the absence of mac-SiO2 results in materials with structural characteristics consistent with the carbon nitride, melon, accompanied by ca. 2 wt% carbonization. For mac-SiO2 supported materials, condensation occurs with greater carbonization (ca. 6 wt%). On addition of 3 wt% Pt cocatalyst photocatalytic hydrogen production under visible light is found to be up to 10 times greater for the supported composites. Time-resolved photoluminescence spectroscopy shows that excited state relaxation is more rapid for the mac-SiO2 supported materials suggesting faster electron-hole recombination and that supported carbon nitride does not exhibit improved charge separation. CO2 temperature programmed desorption indicates that enhanced photoactivity of supported carbon nitride is attributable to an increased surface area compared to bulk carbon nitride and an increase in the concentration of weakly basic catalytic sites, consistent with carbon nitride oligomers.

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We demonstrate a new approach to in-situ measurement of femtosecond laser pulse induced changes in glass enabling the reconstruction in 3D of the induced complex permittivity modification. The technique can be used to provide single shot and time resolved quantitative measurements with a micron scale spatial resolution.

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Recent work has highlighted the potential of sol-gel-derived calcium silicate glasses for the regeneration or replacement of damaged bone tissue. The work presented herein provides new insight into the processing of bioactive calcia-silica sol-gel foams, and the reaction mechanisms associated with them when immersed in vitro in a simulated body fluid (SBF). Small-angle X-ray scattering and wide-angle X-ray scattering (diffraction) have been used to study the stabilization of these foams via heat treatment, with analogous in situ time-resolved data being gathered for a foam immersed in SBF. During thermal processing, pore sizes have been identified in the range of 16.5-62.0 nm and are only present once foams have been heated to 400 degrees C and above. Calcium nitrate crystallites were present until foams were heated to 600 degrees C; the crystallite size varied from 75 to 145 nm and increased in size with heat treatment up to 300 degrees C, then decreased in size down to 95 rim at 400 degrees C. The in situ time-resolved data show that the average pore diameter decreases as a function of immersion time in SBF, as calcium phosphates grow on the glass surfaces. Over the same time, Bragg peaks indicative of tricalcium phosphate were evident after only 1-h immersion time, and later, hydroxycarbonate apatite was also seen. The hydroxycarbonate apatite appears to have preferred orientation in the (h,k,0) direction.

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A femtosecond pump-probe setup was used to measure the time resolved reflectivity of hydrogenated amorphous silicon containing crystalline silicon nanoparticles at eight different incidence angles. Results fitted with the Drude model found a scattering rate of G = 2-1+1.2×1015?s-1 at a corresponding carrier concentration of ~ 1020?cm-3. The observed scattering rate is attributed to enhanced carrier-carrier interaction in optically pumped nanocrystals.

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Synchronous, time-resolved DRIFTS/MS/XAS cycling studies of the vapor-phase selective aerobic oxidation of crotyl alcohol over nanoparticulate Pd have revealed surface oxide as the desired catalytically active phase, with dynamic, reaction-induced Pd redox processes controlling selective versus combustion pathways.

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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

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The aerobic selective oxidation (selox) of alcohols represents an environmentally benign and atom efficient chemical valorisation route to commercially important allylic aldehydes, such as crotonaldehyde and cinnamaldehyde, which find application in pesticides, fragrances and food additives. Palladium nanoparticles are highly active and selective heterogeneous catalysts for such oxidative dehydrogenations, permitting the use of air (or dioxygen) as a green oxidant in place of stoichiometric chromate permanganate saltsor H2O2. Here we discuss how time-resolved, in-situ X-ray spectroscopies (XAS and XPS) reveal dynamic restructuring of dispersed Pd nanoparticles and Pd single-crystals in response to changing reaction environments, and thereby identify surface PdO as the active species responsible for palladium catalysed crotyl alcohol selox (Figure 1); on-stream reduction to palladium metal under oxygen-poor regimes thus appears the primary cause of catalyst deactivation. This insight has guided the subsequent application of surfactant-templating and inorganic nanocrystal methodologies to optimize the density of desired active PdO sites for the selective oxidation of natural products such as sesquiterpenoids.

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The rational design of new heterogeneous catalysts for clean chemical technologies can be accelerated by molecular level insight into surface chemical processes. In-situ methodologies, able to provide time-resolved and/or pressure dependent information on the evolution of reacting adsorbed layers over catalytically relevant surfaces, are therefore of especial interest. Here we discuss the application of in-situ XPS and in-situ, synchronous DRIFTS/MS/XAS methodologies to elucidate the active site in Pd-catalyzed, selective aerobic oxidation of allylic alcohols.