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La1–xSrxCoO3 (x = 0, 0.1, 0.2) and LaCo0.8Fe0.2O3 perovskite nanoparticles were synthesized by spray-flame synthesis, and their electrocatalytic water oxidation activity was evaluated in the prepared state. Highly crystalline, rhombohedrally distorted cubic structures of the cobaltite perovskites were confirmed by STEM and XRD analyses. The decreased JT distortions were observed in the cobaltite perovskite structure upon substitution with Sr, while orthorhombic distortions in Fe-substituted perovskites could explain the changes in their Raman spectra. Debye–Waller factors and coordination numbers from fitted EXAFS data indicate more disordered crystalline structures upon Sr substitution and a lower Co–O coordination number at 20 at% Sr. Thermal characterization of the catalysts by STA coupled with QMS shows higher mass losses in Sr-substituted catalysts, and these results were associated with a higher concentration of carbonate species in these catalysts, which was also confirmed by XPS measurements. Both Fe and Sr substitution lead to higher catalytic OER activity of the cobaltite perovskites with lower overpotentials of about 30–50 mV. The cobaltite perovskite catalyst substituted with 20 at% Sr exhibited the highest OER activity and stable electrocatalytic performance at moderate conditions.

Aerobic cyclohexene oxidation and peroxide decomposition in the liquid phase were performed over a series of CoxFe3−xO4 spinel catalysts exhibiting a volcano plot for the catalytic activity with a maximum at x = 1.

In this study, the temperature and volume fraction distributions of liquid silicon nanoparticles in the aerosol flow in gas-phase synthesis were retrieved using tomographic reconstruction of emission and extinction spectra in the 230–700 nm range. Measurements were done in an optically accessible microwave-plasma flow reactor fed with a SiH4/H2/Ar gas mixture. Optical emission and extinction spectra in the visible spectral range were captured along a line perpendicular to the flow direction covering the entire cross-section of the Si particle stream. Particle temperature and volume fraction distributions were determined and the preferred location of the silicon particles in a 1-mm thick zone at the circumference of the cylindric flow was revealed. The combined recording of line-resolved emission/extinction spectra is a promising method for spatially-resolved detection of nanoparticles in combustion or gas-phase synthesis.

Two-dimensional thermographic particle image velocimetry (T-PIV) is presented for the in situ measurement in optically accessible internal combustion (IC) engines. Temperature and velocity measurements are combined using thermographic phosphor particles as tracers for PIV. For three commercially available phosphors (BAM:Eu2+, ZnO, and ZnO:Zn), temperature sensitivity, luminescence intensity at high temperatures and laser-fluence dependence were evaluated for phosphor-coated surfaces in a high-temperature cell. ZnO:Zn was identified as the best-suited candidate for engine in-cylinder measurements and further analyzed in the aerosolized state at temperatures up to 775 K to generate calibration data required for signal quantification in engine experiments. T-PIV was successfully applied in the IC engine to simultaneously obtain instantaneous two-dimensional velocity and temperature fields using the intensity-ratio method. Despite a measurement uncertainty (±1σ basis) of only 3.7 K at 317 K (1.2%) to 24.4 K (4.2%) at 575 K, this technique suffers from low signal intensities due to thermal quenching at increasing temperatures, which leads to reduced accuracy as the piston approaches top dead center. Thermographic measurements were successful to visualize local temperature changes due to evaporative cooling after fuel injection. The measured mean gas temperatures agreed well with zero-dimensional simulations that use additional wall-temperature measurements from thermographic phosphor measurements based on the lifetime method as input for heat transfer calculations.

La1-x Srx CoO3 (x=0, 0.1, 0.2, 0.3, 0.4) nanoparticles were prepared by spray-flame synthesis and applied in the liquid-phase oxidation of cyclohexene with molecular O2 as oxidant under mild conditions. The catalysts were systematically characterized by state-of-the-art techniques. With increasing Sr content, the concentration of surface oxygen vacancy defects increases, which is beneficial for cyclohexene oxidation, but the surface concentration of less active Co2+ was also increased. However, Co2+ cations have a superior activity towards peroxide decomposition, which also plays an important role in cyclohexene oxidation. A Sr doping of 20 at. % was found to be the optimum in terms of activity and product selectivity. The catalyst also showed excellent reusability over three catalytic runs; this can be attributed to its highly stable particle size and morphology. Kinetic investigations revealed first-order reaction kinetics for temperatures between 60 and 100 °C and an apparent activation energy of 68 kJ mol-1 for cyclohexene oxidation. Moreover, the reaction was not affected by the applied O2 pressure in the range from 10 to 20 bar. In situ attenuated total reflection infrared spectroscopy was used to monitor the conversion of cyclohexene and the formation of reaction products including the key intermediate cyclohex-2-ene-1-hydroperoxide; spin trap electron paramagnetic resonance spectroscopy provided strong evidence for a radical reaction pathway by identifying the cyclohexenyl alkoxyl radical.

Comprehensive characterization of crumpled graphene materials is required to understand their morphologically dependent properties. This study connects the optical properties of crumpled few-layer graphene (FLG) aerosols and colloidal suspensions with particle morphology. The mass absorption cross-section (MAC) of crumpled FLG was measured in the aerosol phase and it is shown that such aerosols absorb visible light more efficiently than soot aerosols. The UV–Vis spectra of FLG suspensions in ethanol were correlated with the mean nanoparticle layer number and the lateral size. The measured optical properties were also simulated using discrete dipole approximation (DDA) applied to volume-reconstructed particles with refractive indices of graphene and graphite from literature. The measurements were more closely reproduced using the refractive index of graphite pellets rather than flat graphene on a substrate. Moreover, we show that a simpler Rayleigh–Debye–Gans (RDG) model can predict the wavelength dependence of the crumpled FLG absorption cross-section.

We demonstrate the first application of a Cr:CdSe laser for highly-sensitive multicomponent intracavity absorption spectroscopy around λ = 3.1-3.4 µm. A detection scheme based on an integrated recording of multiple (∼70) individual Cr:CdSe laser pulses after a single pump-pulse excitation is reported. The sensitivity of our system corresponds to an effective absorption path length of L

We demonstrate the first application of a Cr:CdSe laser for highly-sensitive multicomponent intracavity absorption spectroscopy around λ = 3.1–3.4 µm. A detection scheme based on an integrated recording of multiple (∼70) individual Cr:CdSe laser pulses after a single pump-pulse excitation is reported. The sensitivity of our system corresponds to an effective absorption path length of Leff ≈ 850 m. Exemplary measurements of atmospheric H2O and CH4, and additionally introduced gas-phase HCl, C2H4, or C2H6 are presented. The achieved noise-equivalent detection limits are in the ppb range. Possibilities for further sensitivity enhancement by up to a factor of 104 are discussed.

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We demonstrate how the evaporation properties of gas-borne nanoscale materials, here liquid silicon and germanium nanoparticles, can be obtained through a novel combination of in situ time-resolved...

A polygeneration process with the ability to provide work, heat, and useful chemicals according to the specific demand is a promising alternative to traditional energy conversion systems. By implementing such a process in an internal combustion engine, products like synthesis gas or unsaturated hydrocarbons and very high exergetic efficiencies can be obtained through partial oxidation of natural gas, in addition to the already high flexibility with respect to the required type of energy. To enable compression ignition with natural gas as input, additives such as dimethyl ether are needed to increase the reactivity at low temperatures. In this study, the reaction of fuel-rich natural gas/dimethyl ether (DME) mixtures is investigated to support the further development of reaction mechanisms for these little studied reaction conditions. Temperature-resolved species concentration profiles are obtained by mass spectrometry in a plug-flow reactor at equivalence ratios ϕ = 2, 10, and 20, at temperatures between 473 and 973 K and at a pressure of 6 bar. Ignition delay times and product-gas analyses are obtained from shock-tube experiments, for ϕ = 2 and 10, at 710 – 1639 K and 30 bar. The experimental results are compared to kinetic simulations using two literature reaction mechanisms. Good agreement is found for most species. Reaction pathways are analyzed to investigate the interaction of alkanes and DME. It is found that DME forms radicals at comparatively low temperatures and initiates the conversion of the alkanes. Additionally, according to the reaction pathways, the interaction of the alkanes and DME promotes the formation of useful products such as synthesis gas, unsaturated hydrocarbons and oxygenated species.

Flame synthesis is a powerful and scalable method for generating nanoparticles for a wide range of applications. The chemical interaction of the flame and the precursor combined with the spatial and temporal temperature distribution determine the product properties. For controlled nanoparticle synthesis that can also be scaled to industrial production rates, detailed knowledge of the underlying chemical kinetics and their interaction with the reactive flow is essential. Laser diagnostics has the capability to analyze the process by probing the concentration of important intermediates in shock tubes and reactive flows. The gas-phase synthesis of silica nanoparticles from SiCl4 in a premixed H2/O2 low-pressure flame reactor is studied by laser-induced fluorescence imaging of SiO mole fractions and temperature. The literature value-based spectroscopy model of SiO used for fitting the LIF spectra are validated based on absorption cross-sections measurements in a shock tube, where SiO is formed under precisely defined conditions (temperature, pressure, mole fraction) using a well-known kinetics mechanism for SiH4/CO2/Ar decomposition. Based on literature sources, a reaction mechanism is assembled to describe the oxidation of SiCl4 in the flame, which is then compared to the measured SiO mole fractions distribution to shed light on the current state of the understanding of SiCl4 combustion chemistry and to direct further refinements.

Gas-phase iron compounds strongly affect the flame structure already at very low concentrations, which implies the control of combustion efficiency, pollution formation, and materials synthesis in flames. The impact of iron pentacarbonyl on low-pressure premixed flames was investigated experimentally and numerically for a broad range of equivalence ratios. The burner was operated in top-to-bottom orientation, causing a strong effect of buoyancy on the flow field, a configuration, also known as buoyancy-opposed flame. The application of ultra-sensitive broadband intracavity laser absorption diagnostics enabled path-integrated measurements of gas-phase FeO in the particle-laden flow. Spatially-resolved temperature distributions were measured via OH laser-induced fluorescence. The measurements were complemented by detailed simulations of the down-firing flame to determine the (one-dimensional) flow field on the centerline of the burner. The experimental findings were the basis for extension of existing reaction schemes for iron-doped flames and a new skeletal scheme was proposed. Measured temperatures and normalized FeO concentrations were used to validate both the detailed and the skeletal scheme. The results of the optimization and reduction procedure helped to improve the understanding of the structure of the iron-doped flame and the role of iron-cluster formation in the interaction mechanisms which cause the flame inhibition or promotion by iron-compounds.

Perovskite nanomaterials such as LaMnO3, LaFeO3, and LaCoO3 were synthesized in a spray flame from metal nitrates dissolved in combustible liquids. The addition of low-boiling solvents such as 2-ethylhexanoic acid (2-EHA) to the ethanol-based solutions supports the formation of phase-pure particles with unimodal particle-size distribution in the 10-nm range attributed to enhanced evaporation through micro-explosions. Nevertheless, in many cases, a second particle mode with sizes of a few hundred nanometers is formed. In this paper, we investigate two possible reasons for the appearance of large particles. Firstly, we analyze the effect of the oxygen dispersion gas flow applied in the two-fluid nozzle on the droplet size distributions of burning sprays using phase Doppler anemometry. We identified that an increase of the dispersion gas flow significantly decreases the number concentration of large droplets (>30 μm), which causes a significant increase of the BET surface area of as-synthesized LaMnO3 and LaCoO3 with increasing dispersion gas flow from 60 m2/g (5 slm dispersion gas) to 100 m2/g (8 slm). Secondly, the esterification in the mixture of solvents towards ethyl-2-ethylhexanoate, which is associated with the release of water as a byproduct, was analyzed by GC/MS. The ester concentration in the iron-containing solution was found to be up to nine times higher than in cobalt or manganese precursor solutions. Simultaneously, the produced LaFeO3 materials show lower BET surface areas and the increasing dispersion gas flow has a minor effect on this material than on the cobalt and manganese perovskite cases. We attribute this to the fact that water formed during esterification forces the hydrolysis of iron nitrate and the formation of large particles within the droplets.

We report state-resolved absorption cross-section measurement and oscillator-strength evaluation of the gas-phase iron oxide (FeO) orange system near 611 nm. Intracavity absorption spectroscopy (ICAS) with a homemade broadband dye laser was applied for time-resolved measurements of absorption spectra of shock-activated mixtures of iron pentacarbonyl and carbon dioxide (diluted in argon), generating gas-phase FeO. The measurements were performed with a time resolution of 170 µs in the spectral range of 16,316–16,353 cm−1 that includes a large number of FeO absorption lines. Across the 8-cm diameter of the shock tube, ICAS leads to an effective absorption path length of 260 m. Absorption cross-section values of 0.5 × 10–18–4 × 10–18 cm2 were determined for temperatures around 2200 K and pressures of ∼1.3 bar. Pressure- and temperature-independent oscillator strengths for individual ro-vibronic transitions within the 611-nm band of FeO orange system are reported for the first time. These data are generally applicable for quantitative absorption measurements of flame studies of iron chemistry, where FeO plays a key role as intermediate species.

Ethanol is known to be prone to pre-ignition in internal combustion engines under high-load conditions and its ignition shows large deviations from ideal, spatially, and temporally-homogeneous ignition in shock tubes at moderate temperatures (800–950 K). In this context, the ignition of stoichiometric ethanol/O2 mixtures with various levels of inert gas dilution was investigated in a high-pressure shock tube at ≅20 bar between 800 and 1250 K. Ignition delay times were determined from spatially integral detection of chemiluminescence emission. Additionally, high-repetition-rate color imaging enabled the differentiation of the luminescence in time, space, and spectral range between various ignition modes. In the low-temperature range (800–860 K), different inhomogeneous ignition modes were identified. The addition of small amounts of helium into the undiluted fuel/air mixture was found to be efficient to mitigate pre-ignition, attributed to a variation in heat transfer and thus suppression of the build-up of local temperature inhomogeneities. The experiments in case of spatially homogeneous ignition show very good agreement with the predictions based on three detailed kinetics mechanisms (Zhang et al., CNF 190 (2018) 74, Frassoldati et al., CNF 159 (2012) 2295, and Zhou et al. CNF 197 (2018) 423), inhomogeneities, however, resulted in a shortening of the ignition delay times up to a factor of 2.6.

Shock-tube and flow-reactor experiments were used to study the thermal decomposition of diethyl carbonate (C2H5OC(O)OC2H5; DEC). The formation of CO2, C2H4, and C2H5OH was measured with gas chromatography/mass spectrometry (GC/MS) and high-repetition-rate time-of-flight mass spectrometry (HRR-TOF-MS) behind reflected shock waves. The same products were also detected by GC/MS in flow reactor experiments. All experiments combined span a temperature range of 663–1203 K at pressures between 1.0 and 2.0 bar. Time-resolved species concentration profiles from HRR-TOF-MS and product compositions from GC/MS measurements were simulated applying a detailed reaction mechanism for DEC combustion. A master-equation analysis was conducted based on computed energies from G4 calculations. Quantum chemical calculations confirm that DEC primarily decomposes by six-center elimination, C2H5OC(O)OC2H5 → C2H4 + C2H5OC(O)OH (1a) , followed by rapid decomposition of the alkoxy acid, C2H5OC(O)OH → C2H5OH + CO2 (1b) . Measured DEC decomposition rate constants k(T) at p ≈ 1.5 bar can be represented by the Arrhenius equation k(T) = 1013.64±0.12 exp(−204.24±1.95 kJ/mol/RT) s − 1. Theoretical predictions for k1a were in good agreement with experimentally derived values. The theoretical analysis also included dipropyl carbonate (C3H7OC(O)OC3H7; DPC) decomposition and the reactivities of DEC and DPC are compared and discussed in the context of reactivity of dialkyl carbonates under pyrolytic conditions.

A combinatorial approach was applied to devise a set of reference Si–C–O–H species that is used to derive group-additivity values (GAVs) for this class of molecules. The reference species include 62 stable single-bonded, 19 cyclic, and nine double-bonded Si–C–O–H species. The thermochemistry of these reference species, that is, the standard enthalpy of formation, entropy, and heat capacities covering the temperature range from 298 to 2000 K was obtained from quantum chemical calculations using several composite methods, including G4, G4MP2, and CBSQB3, and the isodesmic reaction approach. To calculate the GAVs from the ab initio based thermochemistry of the compounds in the training set, a multivariable linear regression analysis is performed. The sensitivity of GAVs to the different composite methods is discussed, and thermodynamics properties calculated via group additivity are compared with available ab initio calculated values from the literature.

Ignition delay times (IDTs) of fuel-rich CH4/dimethoxymethane (DMM)/air mixtures (ϕ = 2 and 10) were measured in a high-pressure shock tube at a pressure of 30 bar and compared to simulations based on reaction mechanisms for DMM from literature. Additionally, IDT of DMM/air mixtures were measured at similar conditions in a wide range of equivalence ratios (ϕ = 0.5, 1, and 2). Those mechanisms that predict the IDTs of DMM within the experimental uncertainties also predict the IDTs of the fuel-rich CH4/DMM/air mixtures very well although they were not designed for these conditions. For the measurements at ϕ = 10, product gas samples were extracted from the shock tube test section at around 14–24 ms after arrival of the reflected shock wave by a fast-opening valve and analyzed with gas chromatography. Besides CO, H2, and H2O, ethane, ethylene, acetylene, benzene, propene and toluene were observed as main reaction products.

The oxidation of CH4/diethyl ether mixtures was studied with laser absorption-based time-resolved temperature and CO concentration measurements behind reflected shock waves. Fuel-rich (equivalence ratio ϕ = 2.0) mixtures were studied because of their relevance for mechanism development for partial oxidation reactions in the context of polygeneration processes and measurements at ϕ = 0.5 and 1.0 were used to verify the mechanism performance in an extended range of equivalence ratios. Temperature and CO concentration were measured via absorption using two fundamental vibrations of CO (ν" = 0, P20 and ν" = 1, R21) with two mid-IR quantum-cascade lasers near 4.8546 and 4.5631 µm. Interference from broadband absorption of CO2 in the region near 4.56 µm was quantified based on measured temperature-dependent CO2 absorption cross-sections and mechanism-based prediction of CO2 concentrations. The measured temporal CO-concentration and temperature profiles were compared with simulations based on two mechanisms (Fikri et al., 2017; Yasunaga et al., 2010). For mixtures with ϕ = 0.5, the two mechanisms show similar results, and well reproduce the experimental data. At ϕ = 1.0 and 2.0, the Fikri et al. mechanism shows very good agreement with the experiments whereas the Yasunaga et al. mechanism predicts a too fast CO-concentration and temperature rise.

Tomographic imaging using multi-simultaneous measurements (TIMes) of spontaneous light emission was performed on various operating conditions of the SpraySyn burner to analyse the flame morphology and its potential impact on spray flame pyrolysis. Concurrent instantaneous and time-averaged three-dimensional measurements of CH* chemiluminescence (flame front indicator) and atomic Na emission from NaCl dissolved in the injected combustible liquid (related to hot burnt products of the spray flame) were reconstructed employing a 29-camera setup. Overlapping regions of CH* and Na are presented using isosurface visualisation, local correlation coefficient fields and joint probability distributions. The instantaneous results reveal the complex nature of the reacting flow and regions of interaction between the flame front with the hot gases that originate from the spray stream. The averaged reconstructions show that the spray flames tested are slightly asymmetric near the burner exit but develop into symmetric bell-shaped distributions at downstream locations. The changes in the flame structure for different operating conditions are analysed in light of previous studies, helping in the better understanding of the nanoparticle synthesis process. Furthermore, the importance of using measurements from two views for significantly improved alignment of the burner based on the originally proposed procedure are discussed in light of the reconstructions. This is an important aspect since the SpraySyn is intended for use as a well-defined standardised burner for nanoparticle synthesis, which is being investigated numerically and experimentally across different research groups.

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