Spectroscopic set‐up for simultaneous UV‐Vis/(Q)EXAFS in situ and in operando studies of homogeneous reactions under laboratory conditions

A novel experimental set‐up for in operando studies of homogeneous catalyzed reactions under laboratory conditions has been developed and tested. It combines time‐resolved X‐ray absorption spectroscopy with UV/Vis spectroscopy. The reaction solution is stirred in a vessel and pumped in a circle by a peristaltic free gear‐wheel through a measurement cell. The X‐ray and UV/Vis beams probe the same sample volume of the cell orthogonally. Reactants can be added to the reaction mixture in the course of the measurements and a defined gas atmosphere can be adjusted up to a pressure of 10 bar. The in situ reduction of cerium(IV) ammonium nitrate to cerium(III) by isopropanol is studied as a test reaction with quick‐XANES and UV/Vis measurements with a time resolution of 60 s and 1 s, respectively.     

A large‐volume gas cell for high‐energy X‐ray reflectivity investigations of interfaces under pressure

A cell for the investigation of interfaces under pressure is presented. Given the pressure and temperature specifications of the cell, P≤ 100 bar and 253 K ≤T≤ 323 K, respectively, high‐energy X‐rays are required to penetrate the thick Al₂O₃ windows. The CH₄(gas)/H₂O(liquid) interface has been chosen to test the performance of the new device. The measured dynamic range of the high‐energy X‐ray reflectivity data exceeds 10^?8, thereby demonstrating the validity of the entire experimental set‐up.     

Multi‐use high/low‐temperature and pressure compatible portable chamber for in situ grazing‐incidence X‐ray scattering studies

The multipurpose portable ultra‐high‐vacuum‐compatible chamber described in detail in this article has been designed to carry out grazing‐incidence X‐ray scattering techniques on the BM25‐SpLine CRG beamline at the ESRF. The chamber has a cylindrical form, built on a 360° beryllium double‐ended conflate flange (CF) nipple. The main advantage of this chamber design is the wide sample temperature range, which may be varied between 60 and 1000 K. Other advantages of using a cylinder are that the wall thickness is reduced to a minimum value, keeping maximal solid angle accessibility and keeping wall absorption of the incoming X‐ray beam constant. The heat exchanger is a customized compact liquid‐nitrogen (LN2) continuous‐flow cryostat. LN2 is transferred from a storage Dewar through a vacuum‐isolated transfer line to the heat exchanger. The sample is mounted on a molybdenum support on the heat exchanger, which is equipped with a BORALECTRIC heater element. The chamber versatility extends to the operating pressure, ranging from ultra‐high vacuum (<10^?10 mbar) to high pressure (up to 3 × 10³ mbar). In addition, it is equipped with several CF ports to allocate auxiliary components such as capillary gas‐inlet, viewports, leak valves, ion gun, turbo pump, etc., responding to a large variety of experiment requirements. A movable slits set‐up has been foreseen to reduce the background and diffuse scattering produced at the beryllium wall. Diffraction data can be recorded either with a point detector or with a bi‐dimensional CCD detector, or both detectors simultaneously. The system has been designed to carry out a multitude of experiments in a large variety of environments. The system feasibility is demonstrated by showing temperature‐dependence grazing‐incidence X‐ray diffraction and conductivity measurements on a 20 nm‐thick La_0.7Ca_0.3MnO₃ thin film grown on a SrTiO₃(001) substrate.     

A deformation rig for synchrotron microtomography studies of geomaterials under conditions down to 10 km depth in the Earth

A hard X‐ray transparent triaxial deformation apparatus, called HADES, has been developed by Sanchez Technologies and installed on the microtomography beamline ID19 at the European Radiation Synchrotron Facility (ESRF). This rig can be used for time‐lapse microtomography studies of the deformation of porous solids (rocks, ceramics, metallic foams) at conditions of confining pressure to 100 MPa, axial stress to 200 MPa, temperature to 250°C, and controlled aqueous fluid flow. It is transparent to high‐energy X‐rays above 60 keV and can be used for in situ studies of coupled processes that involve deformation and chemical reactions. The rig can be installed at synchrotron radiation sources able to deliver a high‐flux polychromatic beam in the hard X‐ray range to acquire tomographic data sets with a voxel size in the range 0.7–6.5 µm in less than two minutes.     

Catalysis by hydrogen chloride in the gas‐phase elimination kinetics of 2‐phenyl‐2‐propanol and 3‐methyl‐1‐buten‐3‐ol

A homogeneous, molecular, gas‐phase elimination kinetics of 2‐phenyl‐2‐propanol and 3‐methyl‐1‐ buten‐3‐ol catalyzed by hydrogen chloride in the temperature range 325–386 °C and pressure range 34–149 torr are described. The rate coefficients are given by the following Arrhenius equations: for 2‐phenyl‐2‐propanol log k₁ (s^?1) = (11.01 ± 0.31) ? (109.5 ± 2.8) kJ mol^?1 (2.303 RT)^?1 and for 3‐methyl‐1‐buten‐3‐ol log k₁ (s^?1) = (11.50 ± 0.18) ? (116.5 ± 1.4) kJ mol^?1 (2.303 RT)^?1. Electron delocalization of the CH₂?CH and C₆H₅ appears to be an important effect in the rate enhancement of acid catalyzed tertiary alcohols in the gas phase. A concerted six‐member cyclic transition state type of mechanism appears to be, as described before, a rational interpretation for the dehydration process of these substrates. Copyright © 2007 John Wiley & Sons, Ltd.     

Calibration method at the N K‐edge using interstitial nitrogen gas in solid‐state nitrogen‐containing inorganic compounds

The standard method of soft X‐ray beamline calibration at the N K‐edge uses the ν = 0 peak transition of gas‐phase N₂. Interstitial N₂ gas trapped or formed within widely available solid‐state ammonium‐ and amine‐containing salts can be used for this purpose, bypassing gas‐phase measurements. Evidence from non‐nitrogen‐containing compounds (KH₂PO₄) and from He‐purged ammonium salts suggest that production of N₂ gas is through beam‐induced decomposition. Compounds with nitrate or nitrite as anions produce coincident features and are not suitable for this calibration method.     

Kinetics and mechanisms of gas‐phase decarbonylation of α‐methyl‐trans‐cinamaldehyde and E‐2‐methyl‐2‐pentenal under homogeneous catalysis of hydrogen chloride

The kinetics of the gas‐phase elimination of α‐methyl‐trans‐cinamaldehyde catalyzed by HCl in the temperature range of 399.0–438.7 °C, and the pressure range of 38–165 Torr is a homogeneous, molecular, pseudo first‐order process and undergoing a parallel reaction to produce via (A) α‐methylstyrene and CO gas and via (B) β‐methylstyrene and CO gas. The decomposition of substrate E‐2‐methyl‐2‐pentenal was performed in the temperature range of 370.0–410.0 °C and the pressure range of 44–150 Torr also undergoing a molecular, pseudo first‐order reaction gives E‐2‐pentene and CO gas. These reactions were carried out in a static system seasoned reactions vessels and in the presence of toluene free radical inhibitor. The rate coefficients are given by the following Arrhenius expressions:

• Products formation from α‐methyl‐trans‐cinamaldehyde
• α‐methylstyrene :
• β‐methylstyrene :
• Products formation from E‐2‐methyl‐2‐pentenal
• E‐2‐pentene :

The kinetic and thermodynamic parameters for the thermal decomposition of α‐methyl‐trans‐cinamaldehyde suggest that via (A) proceeds through a bicyclic transition state type of mechanism to yield α‐methylstyrene and carbon monoxide, whereas via (B) through a five‐membered cyclic transition state to give β‐methylstyrene and carbon monoxide. However, the elimination of E‐2‐methyl‐2‐pentenal occurs by way of a concerted cyclic five‐membered transition state mechanism producing E‐2‐pentene and carbon monoxide. The present results support that uncatalyzed α‐β‐unsaturated aldehydes decarbonylate through a three‐membered cyclic transition state type of mechanism. Copyright © 2014 John Wiley & Sons, Ltd.     

miXAFS: a program for X‐ray absorption fine‐structure data analysis

A new program called miXAFS for the analysis of X‐ray absorption fine‐structure (XAFS) data is presented. miXAFS can analyze the XAFS functions simultaneously for all measured X‐ray absorption edges of the constituent elements in a sample under the constraints for the structural parameters over the edges. The program provides a surface plot of the R‐factor as a function of two structural parameters, which is useful to validate the optimized structural parameters. The structural parameters can be obtained from the XAFS data in a few steps using the setting file and batch process. The program, which is coded in MATLAB and freely available, runs on Macintosh and Windows operating systems. It has a graphical user interface and loads experimental data and XAFS functions in a variety of ASCII data formats.     

Kinetics and mechanism of gas‐phase pyrolysis of ylides. Part 3.1 Thermal reactivity of α‐carbonyl‐ and thiocarbonyl‐stabilized methylenetriphenylphosphoranes

Fourteen ketone/thione‐stabilized triphenylphosphonium methylides were subjected to conventional gas‐phase and flash vacuum pyrolysis (FVP). The kinetics of the first‐order thermal gas‐phase reactions of all these compounds were investigated over 360–653 K temperature range. The values of the Arrhenius log A and energy of activation of these ylides averaged 11.52 ± 0.34 s^?1 and 133.20 ± 3.14 kJ mol^?1, respectively. The products of sealed‐tube (static) and FVP were analyzed and compared. A mechanism is proposed to account for the products of reaction. The rate constants [k (s^?1)] of the substrates at 500 K were calculated and used to substantiate the proposed mechanism of pyrolysis, and to rationalize the thermal gas‐phase reactivities of the ylides under study. Copyright © 2010 John Wiley & Sons, Ltd.     

Estimating the absolute flux distribution for a synchrotron X‐ray beam using ionization‐chamber measurements with various filters

It is shown that an extensive set of accurate ionization‐chamber measurements with a primary polychromatic synchrotron X‐ray beam transmitted through various filter combinations/thicknesses can be used to quite effectively estimate the absolute flux distribution. The basic technique is simple but the `inversion' of the raw data to extract the flux distribution is a fundamentally ill‐posed problem. It is demonstrated, using data collected at the Imaging and Medical Beamline (IMBL) of the Australian Synchrotron, that the absolute flux can be quickly and reliably estimated if a suitable choice of filters is made. Results are presented as a function of the magnetic field (from 1.40 to 4.00 T) of the superconducting multi‐pole wiggler insertion device installed at IMBL. A non‐linear least‐squares refinement of the data is used to estimate the incident flux distribution and then comparison is made with calculations from the programs SPECTRA, XOP and spec.exe. The technique described is important not only in estimating flux itself but also for a variety of other, derived, X‐ray properties such as beam quality, power density and absorbed‐dose rate. The applicability of the technique with a monochromatic X‐ray beam for which there is significant harmonic contamination is also demonstrated. Whilst absolute results can also be derived in this monochromatic beam case, relative (integrated) flux values are sufficient for our primary aim of establishing reliable determinations of the percentages of the various harmonic components.     

Effect of strain on gas‐phase basicity of (E)‐1‐methyl‐2‐(1‐methyl‐2‐adamantylidene)adamantane

Steric strain, caused by forced deformation of double bond geometry, has significant impact on alkene reactivity, as was shown by a study of the gas‐phase basicity of (E)‐1‐methyl‐2‐(1‐methyl‐2‐adamantylidene)adamantane. The Gibbs free energy of the strain effect in this compound was 42 kJ/mol. This analysis was made based on adamantylideneadamantane as a congeneric reference compound with a planar double bond. It was concluded that gas‐phase basicity could serve as a valuable alternative indicator for quantification of steric strain in alkenes. Copyright © 2015 John Wiley & Sons, Ltd.     

The high‐resolution absorption spectroscopy branch on the VUV beamline DESIRS at SOLEIL

A VUV absorption spectroscopy facility designed for ultra‐high spectral resolution is in operation as a dedicated branch on the DESIRS beamline at Synchrotron SOLEIL. This branch includes a unique VUV Fourier transform spectrometer (FTS) and a dedicated versatile gas sample chamber. The FTS instrument can cover a large UV–VUV spectral range from 4 to 30 eV, with an ultimate line width of 0.08 cm^?1 on a large spectral window, ΔE/E = 7%, over which all spectral features can be acquired in a multiplex way. The performance can be considered to be a middle ground between broadband moderate‐resolution spectrometers based on gratings and ultra‐high‐spectral‐resolution VUV tunable‐laser‐based techniques over very narrow spectral windows. The various available gaseous‐sample‐handling setups, which function over a wide range of pressures and temperatures, and the acquisition methodology are described. A selection of experimental results illustrates the performance and limitations of the FTS‐based facility.     

Multiple M‐Effect Signal in Noble Gases and Hydrogen Mixture Discharge

The M‐effect (monochromatization‐effect) is a powerful process which can give high intensity monochromatic spectra with a certain wavelength depending on the type of used gas mixtures to generate the plasma state. The effect consists in the emission of a single spectral line emerging from plasma under specific experimental conditions involving one electropositive gas and one electronegative gas mixture. For example, in the case of Ne‐H₂ mixture, a clear monochrome radiation was obtained, corresponding to the λ_Ne =585.3 nm wavelength at 2p₁‐1s₂ transition in the Paschen notation, the pressures ranging between 10‐100 torr. In this paper we prove the general character of this effect, i.e. if the optical emission spectra (OES) reduced to selective lines can be noticed also in other multiple gas mixture discharges. The Ne‐Ar‐Xe mixture discharges with different percentages of H2 as electronegative gas added in has been investigated. The triple M‐effect, means three specific monochromatic lines, could be revealed in the OES at 50% of H2 addition in Ne‐Ar‐Xe mixture (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A computational study of the thermolysis of β‐hydroxy ketones in gas phase and in m‐xylene solution

Theoretical calculations at the M05‐2X/6‐31+G(d) level of theory have been carried out in order to explore the nature of the mechanism of the thermal decomposition reactions of the β‐hydroxy ketones, 4‐hydroxy‐2‐butanone, 4‐hydroxy‐2‐pentanone, and 4‐hydroxy‐2‐methyl‐2‐pentanone in gas phase and in m‐xylene solution. The mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state. A reasonable agreement between experimental and calculated activation parameters and rate constants has been obtained, the tertiary : secondary : primary alcohol rate constant ratio being calculated, at T = 503.15 K, as 5.9:4.7:1.0 in m‐xylene solution and 44.1:5.0:1.0 in the gas phase, compared with the experimental values, 3.7:1.3:1.0 and 13.5:3.2:1.0, respectively. The progress of the thermal decomposition reactions of β‐hydroxy ketones has been followed by means of the Wiberg bond indices. The lengthening of the O₁–C₂ bond with the initial migration of the H₆ atom from O₅ to O₁ can be seen as the driving force for the studied reactions. Calculated synchronicity values indicate that the mechanisms correspond to concerted and highly synchronous processes. The transition states are “advanced”, nearer to the products than to the reactants. Copyright © 2012 John Wiley & Sons, Ltd.     

Adaption of a diffractometer for time‐resolved X‐ray resonant magnetic scattering

A new set‐up is presented to measure element‐selective magnetization dynamics using the ALICE chamber [Grabis et al. (2003), Rev. Sci. Instrum. 74 , 4048–4051] at the BESSY II synchrotron at the Helmholtz‐Zentrum Berlin. A magnetic‐field pulse serves as excitation, and the magnetization precession is probed by element‐selective X‐ray resonant magnetic scattering. With the use of single‐bunch‐generated X‐rays a temporal resolution well below 100 ps is reached. The ALICE diffractometer environment enables investigations of thin films, described here, multilayers and laterally structured samples in reflection or diffuse scattering geometry. The combination of the time‐resolved set‐up with a cryostat in the ALICE chamber will allow temperature‐dependent studies of precessional magnetization dynamics and of damping constants to be conducted over a large temperature range and for a large variety of systems in reflection geometry.     

21.0%‐efficient co‐diffused screen printed n‐type silicon solar cell with rear‐side boron emitter

Plasma enhanced chemical vapor deposition (PECVD) is applied to deposit boron silicate glasses (BSG) acting as boron diffusion source during the fabrication of n‐type silicon solar cells. We characterize the resulting boron‐diffused emitter after boron drive‐in from PECVD BSG by measuring the sheet resistances R_sheet,B and saturation current densities J_0,B. For process optimization, we vary the PECVD deposition parameters such as the gas flows of the precursor gases silane and diborane and the PECVD BSG layer thickness. We find an optimum gas flow ratio of SiH₄/B₂H₆= 8% and layer thickness of 40 nm. After boron drive in from these PECVD BSG diffusion sources, a low J_0,B values of 21 fA/cm² is reached for R_sheet,B = 70 Ω/□. The optimized PECVD BSG layers together with a co‐diffusion process are implemented into the fabrication process of passivated emitter and rear totally diffused (PERT) back junction (BJ) cells on n‐type silicon. An independently confirmed energy conversion efficiency of 21.0% is achieved on 15.6 × 15.6 cm² cell area with a simplified process flow. This is the highest efficiency reported for a co‐diffused n‐type PERT BJ cell using PECVD BSG as diffusion source. A loss analysis shows a small contribution of 0.13 mW/cm² of the boron diffusion to the recombination loss proving the high quality of this diffusion source. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Design and development of a controlled pressure/temperature set‐up for in situ studies of solid–gas processes and reactions in a synchrotron X‐ray powder diffraction station

A novel set‐up has been designed and used for synchrotron radiation X‐ray high‐resolution powder diffraction (SR‐HRPD) in transmission geometry (spinning capillary) for in situ solid–gas reactions and processes in an isobaric and isothermal environment. The pressure and temperature of the sample are controlled from 10^?3 to 1000 mbar and from 80 to 1000 K, respectively. To test the capacities of this novel experimental set‐up, structure deformation in the porous material zeolitic imidazole framework (ZIF‐8) by gas adsorption at cryogenic temperature has been studied under isothermal and isobaric conditions. Direct structure deformations by the adsorption of Ar and N₂ gases have been observed in situ, demonstrating that this set‐up is perfectly suitable for direct structural analysis under in operando conditions. The presented results prove the feasibility of this novel experimental station for the characterization in real time of solid–gas reactions and other solid–gas processes by SR‐HRPD.     

Complex solutions under shear and pressure: a rheometer setup for X‐ray scattering experiments

A newly developed high‐pressure rheometer for in situ X‐ray scattering experiments is described. A commercial rheometer was modified in such a way that X‐ray scattering experiments can be performed under different pressures and shear. First experiments were carried out on hyaluronan, a ubiquitous biopolymer that is important for different functions in the body such as articular joint lubrication. The data hint at a decreased electrostatic interaction at higher pressure, presumably due to the increase of the dielectric constant of water by 3% and the decrease of the free volume at 300 bar.