Near-Surface Gas-Phase Methoxymethanol Is Generated by Methanol Oxidation over Pd-Based Catalysts.

Catalytic conversion of alcohols underlies many commodity and fine chemical syntheses, but a complete mechanistic understanding is lacking. We examined catalytic oxidative conversion of methanol near atmospheric pressure using operando small-aperture molecular beam time-of-flight mass spectrometry, interrogating the gas phase 500 µm above Pd-based catalyst surfaces. In addition to a variety of stable C1-3 species, we detected methoxymethanol (CH3OCH2OH)─a rarely observed and reactive C2 oxygenate that has been proposed to be a critical intermediate in methyl formate production. Methoxymethanol is observed above Pd, AuxPdy alloys, and oxide-supported Pd (common methanol oxidation catalysts). Experiments establish temperature and reactant feed ratio dependences of methoxymethanol generation, and calculations using density functional theory are used to examine the energetics of its likely formation pathway. These results suggest that future development of catalysts and microkinetic models for methanol oxidation should be augmented and constrained to accommodate the formation, desorption, adsorption, and surface reactions involving methoxymethanol.

Advances in imaging of chemically reacting flows.

Many important chemically reacting systems are inherently multi-dimensional with spatial and temporal variations in the thermochemical state, which can be strongly coupled to interactions with transport processes. Fundamental insights into these systems require multi-dimensional measurements of the thermochemical state as well as fluid dynamics quantities. Laser-based imaging diagnostics provide spatially and temporally resolved measurements that help address this need. The state of the art in imaging diagnostics is continually progressing with the goal of attaining simultaneous multi-parameter measurements that capture transient processes, particularly those that lead to stochastic events, such as localized extinction in turbulent combustion. Development efforts in imaging diagnostics benefit from advances in laser and detector technology. This article provides a perspective on the progression of increasing dimensionality of laser-based imaging diagnostics and highlights the evolution from single-point measurements to 1D and 2D multi-parameter imaging and 3D high-speed imaging. This evolution is demonstrated using highlights of laser-based imaging techniques in combustion science research as an exemplar of a complex multi-dimensional chemically reacting system with chemistry-transport coupling. Imaging diagnostics impact basic research in other chemically reacting systems as well, such as measurements of near-surface gases in heterogeneous catalysis. The expanding dimensionality of imaging diagnostics leads to larger and more complex datasets that require increasingly demanding approaches to data analysis and provide opportunities for increased collaboration between experimental and computational researchers in tackling these challenges.

phi2FLIM: a technique for alias-free frequency domain fluorescence lifetime imaging.

A new approach to alias-free wide-field fluorescence lifetime imaging in the frequency domain is demonstrated using a supercontinuum source for fluorescence excitation and a phase-modulated image intensifier for detection. This technique is referred to as phi-squared fluorescence lifetime imaging (phi(2)FLIM). The phase modulation and square-wave gating of the image intensifier eliminate aliasing by the effective suppression of higher harmonics. The ability to use picosecond excitation pulses without aliasing expands the range of excitation sources available for frequency-domain fluorescence lifetime imaging (fd-FLIM) and improves the modulation depth of conventional homodyne fd-FLIM measurements, which use sinusoidal intensity modulation of the excitation source. The phi(2)FLIM results are analyzed using AB-plots, which facilitate the identification of mono-exponential and multi-exponential fluorescence decays and provide measurements of the fluorophore fractions in two component mixtures. The rapid acquisition speed of the technique enables lifetime measurements in dynamic systems, such as temporally evolving samples and samples that are sensitive to photo-bleaching. Rapid phi(2)FLIM measurements are demonstrated by imaging the dynamic mixing of two different dye solutions at 5.5 Hz. The tunability of supercontinuum radiation enables excitation wavelength resolved FLIM measurements, which facilitates analysis of samples containing multiple fluorophores with different absorption spectra.

Comparison of nanosecond and picosecond excitation for interference-free two-photon laser-induced fluorescence detection of atomic hydrogen in flames.

Two-photon laser-induced fluorescence (TP-LIF) line imaging of atomic hydrogen was investigated in a series of premixed CH4/O2/N2, H2/O2, and H2/O2/N2 flames using excitation with either picosecond or nanosecond pulsed lasers operating at 205 nm. Radial TP-LIF profiles were measured for a range of pulse fluences to determine the maximum interference-free signal levels and the corresponding picosecond and nanosecond laser fluences in each of 12 flames. For an interference-free measurement, the shape of the TP-LIF profile is independent of laser fluence. For larger fluences, distortions in the profile are attributed to photodissociation of H2O, CH3, and/or other combustion intermediates, and stimulated emission. In comparison with the nanosecond laser, excitation with the picosecond laser can effectively reduce the photolytic interference and produces approximately an order of magnitude larger interference-free signal in CH4/O2/N2 flames with equivalence ratios in the range of 0.5< or =Phi< or =1.4, and in H2/O2 flames with 0.3< or =Phi< or =1.2. Although photolytic interference limits the nanosecond laser fluence in all flames, stimulated emission, occurring between the laser-excited level, H(n=3), and H(n=2), is the limiting factor for picosecond excitation in the flames with the highest H atom concentration. Nanosecond excitation is advantageous in the richest (Phi=1.64) CH4/O2/N2 flame and in H2/O2/N2 flames. The optimal excitation pulse width for interference-free H atom detection depends on the relative concentrations of hydrogen atoms and photolytic precursors, the flame temperature, and the laser path length within the flame.

Use of Rayleigh imaging and ray tracing to correct for beam-steering effects in turbulent flames.

Laser Rayleigh imaging has been applied in a number of flow and flame studies to measure concentration or temperature distributions. Rayleigh cross sections are dependent on the index of refraction of the scattering medium. The same index of refraction changes that provide contrast in Rayleigh images can also deflect the illuminating laser sheet. By applying a ray-tracing algorithm to the detected image, it is possible to correct for some of these beam-steering effects and thereby improve the accuracy of the measured field. Additionally, the quantification of the degree of beam steering through the flow provides information on the degradation of spatial resolution in the measurement. Application of the technique in a well-studied laboratory flame is presented, along with analysis of the effects of image noise and spatial resolution on the effectiveness of the algorithm.

Comparison of nanosecond and picosecond excitation for two-photon laser-induced fluorescence imaging of atomic oxygen in flames.

Two-photon laser-induced fluorescence (LIF) imaging of atomic oxygen is investigated in premixed hydrogen and methane flames with nanosecond and picosecond pulsed lasers at 226 nm. In the hydrogen flame, the interference from photolysis is negligible compared with the LIF signal from native atomic oxygen, and the major limitations on quantitative measurements are stimulated emission and photoionization. Excitation with a nanosecond laser is advantageous in the hydrogen flames, because it reduces the effects of stimulated emission and photoionization. In the methane flames, however, photolytic interference is the major complication for quantitative O-atom measurements. A comparison of methane and hydrogen flames indicates that vibrationally excited CO2 is the dominant precursor for laser-generated atomic oxygen. In the methane flames, picosecond excitation offers a significant advantage by dramatically reducing the photolytic interference. The prospects for improved O-atom imaging in hydrogen and hydrocarbon flames are presented.