High temperature protonic conduction in Sr-doped LaP3O9

Electrical conduction of Sr-doped LaP₃O₉ ([Sr]/{[La] + [Sr]} = 2–10 mol%) was investigated under 0.4–5 kPa of p(H₂O) and 0.01–100 kPa of p(O₂) or 0.3–3 kPa of p(H₂) at 573–973 K. Sr-doped LaP₃O₉ showed apparent H/D isotope effect on conductivity regardless of the Sr-doping level under both H₂O/O₂ oxidizing and H₂/H₂O reducing conditions at investigated temperatures. Conductivities of the material were almost independent of p(O₂) and p(H₂O). These results demonstrated that the Sr-doped LaP₃O₉ exhibited protonic conduction under wide ranges of p(O₂), p(H₂O) and temperature. The conductivity of the Sr-doped LaP₃O₉ increased with increasing Sr concentration up to its solubility limit, ca. 3 mol%, while the further Sr-doping slightly degraded the conductivity. These indicate that Sr²⁺ substitution for La³⁺ leads to proton dissolution into the material and induced protonic conduction. Conductivities of the 3 mol% Sr-doped sample were 2 × 10^- 6–5 × 10^− 4 S cm^− 1 at 573–973 K.     

CRDS of water vapor at 0.1 Torr between 6886 and 7406 cm−1

The absorption spectrum of water vapor in “natural” isotopic abundance has been recorded by high sensitivity CW-Cavity Ring Down Spectroscopy (CW-CRDS) between 6885.79 and 7405.91 cm^?1. This strong absorbing region includes the first hexad of interacting vibrational bands which was previously studied by Fourier Transform Spectroscopy. The achieved sensitivity of the recordings varies from α_min～2×10^–11 to 2×10^?10 cm^?1 allowing us to use a sample pressure of 0.1 Torr, making pressure broadening of the line profile mostly negligible. Weak lines in the vicinity of much stronger lines could then be accurately measured. The weakest lines have intensity on the order of 5×10^–28 cm/molecule at 296 K. A set of 4471 lines were assigned to 4916 transitions of five water isotopologues (H₂ ¹⁶O, H₂ ¹⁸O, H₂ ¹⁷O, HD¹⁶O and HD¹⁸O). A small number of new energy levels was determined mostly for the H₂ ¹⁷O isotopologue. The previous investigations and existing databases are critically evaluated. In particular, a number of corrections and new assignments are proposed for the water list provided by the HITRAN database in the considered region. As a result, a complete list of 12,700 transitions for water in “natural” isotopic abundance is provided as Supplementary Material for the 6885–7408 cm^?1 region.     

Fe-based perovskite-type oxides as excellent oxygen-permeable and reduction-tolerant materials

Development of new mixed conductors with both high oxygen permeability and phase stability under reducing atmosphere is indispensable for realizing practical MIEC systems of oxygen separation and membrane reactor. In this study, a family of Co-free Fe-based perovskite-type oxides, (Ba,Sr)(Fe,Mn)O_3−δ was prepared and their oxygen permeability and phase stability against reduction were examined. Optimum Ba doping concentration at A site was found around 30%, and Ba_0.3Sr_0.7FeO_3−δ showed highest oxygen permeability (3.0 cm³(STP)cm^− 2 min^− 1 at 900 °C) in this study. Perovskite-type oxides of the Ba–Mn–Fe–O and Ba–Sr–Mn–Fe–O systems with appropriate compositions preserved the structure even after annealing in the reducing atmosphere of 5% H₂/N₂ at 1000 °C, showing their exceeding reduction tolerance.     

Modeling midwave infrared muzzle flash spectra from unsuppressed and flash-suppressed large caliber munitions

Time-resolved infrared spectra of firings from a 152 mm howitzer were acquired over an 1800–6000 cm^?1 spectral range using a Fourier-transform spectrometer. The instrument collected primarily at 32 cm^?1 spectral and 100 Hz temporal resolutions. Munitions included unsuppressed and chemically flash suppressed propellants. Secondary combustion occurred with unsuppressed propellants resulting in flash emissions lasting ～100 ms and dominated by H₂O and CO₂ spectral structure. Non-combusting plume emissions were one-tenth as intense and approached background levels within 20–40 ms. A low-dimensional phenomenological model was used to reduce the data to temperatures, soot absorbances, and column densities of H₂O, CO₂, CH₄, and CO. The combusting plumes exhibit peak temperatures of ～1400 K, areas of greater than 32 m², low soot emissivity of ～0.04, with nearly all the CO converted to CO₂. The non-combusting plumes exhibit lower temperatures of ～1000 K, areas of ～5 m², soot emissivity of greater than 0.38 and CO as the primary product. Maximum fit residual relative to peak intensity are 14% and 8.9% for combusting and non-combusting plumes, respectively. The model was generalized to account for turbulence-induced variations in the muzzle plumes. Distributions of temperature and concentration in 1–2 spatial regions demonstrate a reduction in maximum residuals by 40%. A two-region model of combusting plumes provides a plausible interpretation as a ～1550 K, optically thick plume core and ～2550 K, thin, surface-layer flame-front. Temperature rate of change was used to characterize timescales and energy release for plume emissions. Heat of combustion was estimated to be ～5 MJ/kg.     

CO2 pressure broadening and shift coefficients for the 1–0 band of HCl and DCl

CO₂ broadened spectra of the 1–0 band of H³⁵Cl and H³⁷Cl, observed near 2886 cm^?1, and the 1–0 band of D³⁵Cl and D³⁷Cl, located near 2089 cm^?1, have been recorded at room temperature and five total pressures between 150 and 700 Torr, using a Bruker IFS125HR Fourier transform spectrometer. Spectra of pure HCl were also recorded. CO₂ broadening and shift coefficients of HCl and DCl have been measured using multi-spectrum non-linear least squares fitting of Voigt profiles. The analysis of the 1–0 band of DCl was complicated by the presence of overlapping CO₂ bands, which were included in the treatment as absorption coefficients calculated taking line-mixing effects into account.     

CO and H2O adsorption and reaction on Au(310)

We have studied desorption of ¹³CO and H₂O and desorption and reaction of coadsorbed, ¹³CO and H₂O on Au(310). From the clean surface, CO desorbs mainly in, two peaks centered near 140 and 200 K. A complete analysis of desorption spectra, yields average binding energies of 21 ± 2 and 37 ± 4 kJ/mol, respectively. Additional desorption states are observed near 95 K and 110 K. Post-adsorption of H₂O displaces part of CO pre-adsorbed at step sites, but does not lead to CO oxidation or significant shifts in binding energies. However, in combination with electron irradiation, ¹³CO₂ is formed during H₂O desorption. Results suggest that electron-induced decomposition products of H₂O are sheltered by hydration from direct reaction with CO.     

Line lists for H218O and H217O based on empirical line positions and ab initio intensities

New line lists for isotopically substituted water are presented. Most line positions were calculated from experimentally determined energy levels, while all line intensities were computed using an ab initio dipole moment surface. Transitions for which experimental energy levels are unavailable use calculated line positions. These line lists cover the range 0.05–20 000 cm^?1 and are significantly more complete and potentially more accurate than the line lists available via standard databases. All lines with intensities (scaled by isotopologue abundance) greater than 10^?29 cm/molecule at 296 K are included, augmented by weaker lines originating from pure rotational transitions. The final line lists contain 39 918 lines for H₂¹⁸O and 27 546 for H₂¹⁷O and are presented in standard HITRAN format. The number of experimentally determined H₂¹⁸O and H₂¹⁷O line positions is, respectively, 32 970 (83% of the total) and 17 073 (62%) and in both cases the average estimated uncertainty is 2×10^?4 cm^?1. The number of ab initio line intensities with an estimated uncertainty of 1% is 16 621 (42%) for H₂¹⁸O and 13 159 (48%) for H₂¹⁷O.     

Surface modification of Ni and Co metal nanowires through MeV high energy ion irradiation

Nickel (Ni) and cobalt (Co) metal nanowires were fabricated by using an electrochemical deposition method based on an anodic alumina oxide (Al₂O₃) nanoporous template. The electrolyte consisted of NiSO₄ · 6H₂O and H₃BO₃ in distilled water for the fabrication of Ni nanowires, and of CoSO₄ · 7H₂O with H₃BO₃ in distilled water for the fabrication of the Co ones. From SEM and TEM images, the diameter and length of both the Ni and Co nanowires were measured to be ∼ 200 nm and 5–10 μm, respectively. We observed the oxidation layers in nanometer scale on the surface of the Ni and Co nanowires through HR–TEM images. The 3 MeV Cl²⁺ ions were irradiated onto the Ni and Co nanowires with a dose of 1 × 10¹⁵ ions/cm². The surface morphologies of the pristine and the 3 MeV Cl²⁺ ion-irradiated Ni and Co nanowires were compared by means of SEM, AFM, and HR–TEM experiments. The atomic concentrations of the pristine and the 3 MeV Cl²⁺ ion-irradiated Ni and Co nanowires were investigated through XPS experiments. From the results of the HR–TEM and XPS experiments, we observed that the oxidation layers on the surface of the Ni and Co nanowires were reduced through 3 MeV Cl²⁺ ion irradiation.     

Ground-based solar absorption studies for the Carbon Cycle science by Fourier Transform Spectroscopy (CC-FTS) mission

Carbon cycle science by Fourier transform spectroscopy (CC-FTS) is an advanced study for a future satellite mission. The goal of the mission is to obtain a better understanding of the carbon cycle in the Earth's atmosphere by monitoring total and partial columns of CO₂, CH₄, N₂O, and CO in the near infrared. CO₂, CH₄, and N₂O are important greenhouse gases, and CO is produced by incomplete combustion. The molecular O₂ column is also needed to obtain the effective optical path of the reflected sunlight and is used to normalize the column densities of the other gases. As part of this advanced study, ground-based Fourier transform spectra are used to evaluate the spectral region and resolution needed. Spectra in the 3950–7140 cm^?1 region with a spectral resolution of 0.0042 cm^?1 recorded at Kiruna (67.84°N, 20.41°E, and 419 m above sea level), Sweden, on 1 April 1998, were degraded to the resolutions of 0.01, 0.1, and 0.3 cm^?1. The effect of spectral resolution on the retrievals has been investigated with these four Kiruna spectra. To obtain further information on the spectral resolution, optical components and spectroscopic parameters required by the future mission, high-resolution solar absorption spectra between 2000 and 15000 cm^?1 were recorded using Fourier transform spectrometers at Kitt Peak (31.9°N, 111.6°W, and 2.1 km above sea level), Arizona, on 25 July 2005 and Waterloo (43.5°N, 80.6°W, and 0.3 km above sea level), Ontario, on 22 November 2006 with spectral resolutions of 0.01 and 0.1 cm^?1, respectively. Dry air volume mixing ratios (VMRs) of CO₂ and CH₄ were retrieved from these ground-based observations. The HITRAN 2004 spectroscopic parameters are used with the SFIT2 package for the spectral analysis. The measurement precisions for CO₂ and CH₄ total columns are better than 1.07% and 1.13%, respectively, for our observations. Based on these results, a Fourier transform spectrometer (maximum spectral resolution of 0.1 cm^?1 or 5 cm maximum optical path difference (MOPD)) operating between 2000 and 15000 cm^?1 is suggested as the primary instrument for the mission. Further progress in improving the atmospheric retrievals for CO₂, CH₄, and O₂ requires new laboratory measurements of the spectroscopic line parameters.     

Baeyer–Villiger oxidation of cyclohexanone to ε-caprolactone in airlift sonochemical reactor

Baeyer–Villiger oxidation of cyclohexanone to ε-caprolactone was studied in a new type reactor – the airlift loop sonochemical reactor. The reactor plays a synergistic effect of sonochemsity and higher oxygen transfer rate. The influences of ultrasound intensity, reaction temperature, the molar ratio of benzaldehyde to cyclohexanone and oxygen gas flow rate on the conversion and selectivity of cyclohexanone were investigated and discussed. Under ultrasound, the amount of benzaldehyde can be reduced from 75% to 67%. Ultrasound not only intensified the rates of reactions but also increased the yield of product. The optimized operation conditions are listed as follows: the reaction temperature is 30 °C, the molar ratio of cyclohexanone to benzaldehyde is 1:2, the oxygen gas flow rate is 1.15 cm s⁻¹, and ultrasonic irradiations 2 h at 40 kHz, 2.25 W cm⁻². Under the optimum operation conditions, the average molar yield of ε-caprolactone comes up to 87.7%.     

Ultrasound assisted co-precipitation of nanostructured CuO–ZnO–Al2O3 over HZSM-5: Effect of precursor and irradiation power on nanocatalyst properties and catalytic performance for direct syngas to DME

Nanostructured CuO–ZnO–Al₂O₃/HZSM-5 was synthesized from nitrate and acetate precursors using ultrasound assisted co-precipitation method under different irradiation powers. The CuO–ZnO–Al₂O₃/HZSM-5 nanocatalysts were characterized using XRD, FESEM, BET, FTIR and EDX Dot-mapping analyses. The results indicated precursor type and irradiation power have significant influences on phase structure, morphology, surface area and functional groups. It was observed that the acetate formulated CuO–ZnO–Al₂O₃/HZSM-5 nanocatalyst have smaller CuO crystals with better dispersion and stronger interaction between components in comparison to nitrate based nanocatalysts. Ultrasound assisted co-precipitation synthesis method resulted in nanocatalyst with more uniform morphology compared to conventional method and increasing irradiation power yields smaller particles with better dispersion and higher surface area. Additionally the crystallinity of CuO is lower at high irradiation powers leading to stronger interaction between metal oxides. The nanocatalysts performance were tested at 200–300 °C, 10–40 bar and space velocity of 18,000–36,000 cm³/g h with the inlet gas composition of H₂/CO = 2/1 in a stainless steel autoclave reactor. The acetate based nanocatalysts irradiated with higher levels of power exhibited better reactivity in terms of CO conversion and DME yield. While there is an optimal temperature for CO conversion and DME yield in direct synthesis of DME, CO conversion and DME yield both increase with the pressure increase. Furthermore ultrasound assisted co-precipitation method yields more stable CuO–ZnO–Al₂O₃/HZSM-5 nanocatalyst while conventional precipitated nanocatalyst lost their activity ca. 18% and 58% in terms of CO conversion and DME yield respectively in 24 h time on stream test.     

Evaluation of ionic conductivity for Mg–Al layered double hydroxide intercalated with inorganic anions

This study demonstrates that humidity, temperature, and the interlayer anions influence ionic conductivities of Mg–Al layered double hydroxides (LDHs) intercalated with inorganic anions. Results show that Mg–Al LDH intercalated with Br^? exhibited the highest ionic conductivity among Mg–Al LDHs intercalated with CO₃^2?, Cl^?, Br^?, NO₃^? and SO₄^2?. Its ionic conductivity was 1.1 × 10^? 2 S cm^? 1 at 80 °C under 80% relative humidity. The electromotive force for the hydroxide ion concentration cell using Mg?Al CO₃^2? LDH showed the same behavior with that using an anion exchange membrane, indicating that Mg–Al CO₃^2? LDH can be a hydroxide ion conductor.     

Protonic mobility in acidic colloids

Colloidal monoclinic zirconia ZrO₂ particles have been synthesized by hydrothermal treatment from acetate solutions. To increase their surface acidity, they have been treated by aqueous solutions of phosphoric acid, sulfophenylphosphonic acid (SPPA, (HO)₂(O)–C₆H₆–SO₃H) and sulfodifluoromethylphosphonic acid (SFPA, (HO)₂(O)P–CF₂–SO₃H). This leads to the covalent bonding of phosphoric or sulfonic acid groups onto the surface of the particles. Solid state NMR (³¹P, ¹H) studies show the covalent grafting of the phosphate and phosphonates groups and qualitatively illustrate the fast proton dynamics of these surface conducting materials as compared with that of crystalline α-Zr(HPO₄)₂. H₂O. But, water adsorption is still necessary to increase the long distance proton mobility. Then, the macroscopic conductivity remains low (between 10^− 4 S cm^− 1 and 10^− 3 S cm^− 1 25 °C, RH 70%) and shows a strong hysteresis while cycling the relative humidity. The mechanism limiting the conductivity seems to be interparticle transfer.     

Ultrasound assisted synthesis of performic acid in a continuous flow microstructured reactor

The present work establishes in depth study of ultrasound assisted preparation of performic acid (PFA) in a continuous flow microstructured reactor. The influence of various parameters viz. formic acid: hydrogen peroxide molar ratio, flow rate, temperature and catalyst loading on the PFA formation were studied in a continuous flow microstructured reactor. In a continuous microstructured reactor in the presence of ultrasonic irradiation, the formation of PFA was found to be dependent on the molar ratio of formic acid: hydrogen peroxide, flow rate of reactants, temperature and catalyst loading (Amberlite IR-120H). The optimized parameter values are 1:1 M ratio, 50 mL/h, 40 °C and 471 mg/cm³ respectively. Further, the performance of Amberlite IR-120H catalyst was evaluated for three successive cycles in continuous microstructured reactor. The performance of catalyst was found to be decreased with the usage of the catalyst and is attributed to neutralization of the sulfonic acid groups, catalyst shrinkage, or loss in pore sites. The experimental results revealed that, for an ultrasound assisted synthesis of PFA in continuous microstructured reactor the observed reaction time was even less than 10 min. The observed intensification in the PFA synthesis process can be attributed to the intense collapse of the cavities formed at low temperature during ultrasonic irradiations, which further improved the heat and mass transfer rates with the formation of H₂O₂ during the reaction. The combined use of ultrasound and a continuous flow microstructured reactor has proved beneficial process of performic acid synthesis.     

Hole polaron of small radius in assemblies of hydrated mono-protonated meso-tetraphenylporphine dimers at 77 K

Polaron theory is often used for the study of electrons and holes mobility in semiconductors when longitudinal optical (LO) phonons are generated upon the charge carriers moving. The polaron theory was applied to explain long-wavelength absorptions observed nearby Soret band in the electronic spectra of assemblies of mono-protonated meso-tetraphenylporphine dimer (TPP₂H⁺) that are interpreted as LO-phonons originated due to proton movement. The energy of hole polaron is found to be 1.50 eV at 77 K. Energy of Franck–Condon transitions of LO-phonons generated by hole polaron moving through water confined in the assemblies with distortions of O–H bonds is 0.2653 eV (2138 cm⁻¹). A broad band around 2127 cm⁻¹ corresponding the same energy of O–H bonds vibrations is observed in IR spectra of the assemblies consisting of water and mainly of TPP₂H⁺ species in the solid state indicating the presence of similar distortions of the hydrogen bonds. The radius of protonic sphere of 0.202 Å, which was estimated as a polaron quasiparticle moving through the confined water at 77 K, is found in agreement with earlier evaluated one of 0.265 Å that was obtained for proton diffusion at 298 K in similar assemblies.     

Critical evaluation of measured rotation–vibration transitions and an experimental dataset of energy levels of HD18O

All available transitions from microwave to visible region (0.2–12 105 cm^?1) of the HD¹⁸O molecule were collected and tested using the RITZ computer code. Literature data were completed by transitions assigned to HD¹⁸O in long path Fourier transform absorption spectra of the H₂O, HDO and D₂O gas mixtures with natural abundance of oxygen-18. In addition about 40 unassigned lines between 4200 and 6600 cm^?1 of our previous water study associated with the HD¹⁸O molecule have been found and assigned. The new long path absorption spectra of the HDO and D₂O mixtures allow us to observe about 1000 transitions of HD¹⁸O in the 6125–10 720 cm^?1 spectral region. These data have been critically analyzed and used to obtain the most complete and precise set of the experimental energy levels of this molecule.     

Ultrasound-assisted acid hydrolysis of cellulose to chemical building blocks: Application to furfural synthesis

In this work, the use of ultrasound energy for the production of furanic platforms from cellulose was investigated and the synthesis of furfural was demonstrated. Several systems were evaluated, as ultrasound bath, cup horn and probe, in order to investigate microcrystalline cellulose conversion using simply a diluted acid solution and ultrasound. Several acid mixtures were evaluated for hydrolysis, as diluted solutions of HNO₃, H₂SO₄, HCl and H₂C₂O₄. The influence of the following parameters in the ultrasound-assisted acid hydrolysis (UAAH) were studied: sonication temperature (30 to 70 °C) and ultrasound amplitude (30 to 70% for a cup horn system) for 4 to 8 mol L⁻¹ HNO₃ solutions. For each evaluated condition, the products were identified by ultra-performance liquid chromatography with high-resolution time-of-flight mass spectrometry (UPLC-ToF-MS), which provide accurate information regarding the products obtained from biomass conversion. The furfural structure was confirmed by nuclear magnetic resonance (¹H and ¹³C NMR) spectroscopy. In addition, cellulosic residues from hydrolysis reaction were characterized using scanning electron microscopy (SEM), which contributed for a better understanding of physical-chemical effects caused by ultrasound. After process optimization, a 4 mol L⁻¹ HNO₃ solution, sonicated for 60 min at 30 °C in a cup horn system at 50% of amplitude, lead to 78% of conversion to furfural. This mild temperature condition combined to the use of a diluted acid solution represents an important contribution for the selective production of chemical building blocks using ultrasound energy.     

Proton transfer in water–hydroxyl mixed overlayers on Pt(1 1 1): Combined approach of laser desorption and spatially-resolved X-ray photoelectron spectroscopy

Proton transfer in water–hydroxyl mixed overlayers on a Pt(1 1 1) surface was studied by a combination of laser induced thermal desorption (LITD) method and spatially-resolved X-ray photoelectron spectroscopy (micro-XPS). The modulated pattern OH + H₂O/H₂O/OH + H₂O was initially prepared by the LITD method; vacant area with a 400 μm width was first formed in the mixed OH + H₂O overlayer by irradiation of focused laser pulses, and followed by refilling the vacant area with pure H₂O. Spatial distribution changes of OH and H₂O were measured as a function of time with the micro-XPS technique, which indicated that H₂O molecules in the central region flow into the OH + H₂O region. From quantitative analyses using a diffusion equation, we found that the proton transfer in the mixed overlayer consists of at least two pathways: direct proton transfer from H₂O to OH in the nearest site and the proton transfer to the next-nearest site via H₃O⁺ formation. The time scale of first and second path was estimated to be 5.2 ± 0.9 ns and 48 ± 12 ns at 140 K, respectively. In the presence of water capping layer, however, the rate of proton transfer is reduced by an order of magnitude, which would be explained by peripatetic behavior of proton into H₂O capping layer.     

High resolution emission spectroscopy of the E2Π–X2Σ+ transition of SrH and SrD

Emission spectra of SrH and SrD have been studied at high resolution using a Fourier transform spectrometer. The molecules have been produced in a high temperature furnace from the reaction of strontium metal vapor with H₂/D₂ in the presence of a slow flow of Ar gas. The spectra observed in the 18 000–19 500 cm^?1 region consist of the 0–0 and 1–1 bands of the E²Π–X²Σ⁺ transition of the two isotopologues. A rotational analysis of these bands has been obtained by combining the present measurements with previously available pure rotation and vibration–rotation measurements for the ground state, and improved spectroscopic constants have been obtained for the E²Π state. The present analysis provides spectroscopic constants for the E²Π state as ΔG(½) = 1166.1011(15) cm^?1, B_e = 3.805503(32) cm^?1, α_e = 0.098880(47) cm^?1, r_e = 2.1083727(89) Å for SrH, and ΔG(½) = 839.1283(23) cm^?1, B_e = 1.918564(15) cm^?1, α_e = 0.034719(23) cm^?1, r_e = 2.1121943(83) Å for SrD.     

Comparing reaction orders of anthracite chars with bituminous coal chars at high temperature oxidation conditions

The influence of concentration of oxygen on the oxidation rates of 5 anthracite chars is investigated at gas temperatures ranging from 1223 K to 1673 K. Reaction orders and kinetic parameters are determined with a multivariable optimization method in which modeled burnout profiles are fitted to experimental burnout profiles from a 4 m isothermal plug flow reactor operating at industrially realistic heating rates, i.e., 10⁴–10⁵ K/s. The determined reaction orders are compared to reaction orders of 10 bituminous coal chars investigated at similar conditions in a previous study. The results show that the optimized reaction order of the anthracite chars is zero, while the reaction order of the bituminous coal char is one. The difference in the reaction orders cannot be explained by using the two semi-global oxidation reactions: C(O) + O₂ → CO/CO₂ and C(O) → CO. However, by also considering 2C(O) → CO₂ + C as a possible reaction step, the reaction order difference between the anthracite chars and the bituminous coal chars can be explained. In addition, a first attempt to apply the same multivariable optimization method to determine the reaction order for a biomass char is presented.