Pretreatment Effect on Pt/CeO2 Catalyst in the Selective Hydrodechlorination of Trichloroethylene

Pt-ceria catalysts present different surface chemistries depending on the preparation method and the pretreatment. The catalytic behavior of Pt/CeO2 catalysts in the hydrodechlorination of trichloroethylene (TCE) to ethylene was examined as a function of the pretreatment conditions and the noble metal precursor salts. Using FTIR and X-ray photoelectron spectroscopy, significant differences were observed in the surface properties of Pt/CeO2 prepared from the H2PtCl6 precursor after different pretreatment procedures (i.e.. reduction or oxidation-reduction). These surface changes are related to chloride residues from the synthesis. Strong changes were observed in the selectivity of the catalysts to ethylene depending on the pretreatment conditions. The 0.5%Pt/CeO2 catalyst showed a 13% selectivity toward ethylene after reduction, whereas alter oxidation, followed by reduction, the selectivity increased up to 85% at the same conversion level. This effect was only observed when a chloride-containing precursor was used in the preparation. In this way, it is demonstrated that the use of a Cl-containing Pt precursor and an air treatment prior to reduction strongly improves the ethylene selectivity of Pt-CeO2 dechlorination catalysts. This can be explained by formation or a CeOCl phase during the synthesis that decomposes upon air tempering, producing oxygen vacancies on the ceria support. We propose that these oxygen vacancies are active for cleaving off Cl from the TCE. Pt then supplies II to clean-off Cl as HCl. Reaction of TCE on Pt produces rather ethane, so Pt may be partly Cl-poisoned for the hydrodechlorination reaction but not for II, dissociation or CO adsorption.

Factors influencing patients with stage 5 chronic kidney disease to opt for conservative management: a practitioner research study

Aims and objectives. This study explored decision-making experiences of patients with stage 5 chronic kidney disease when opting for conservative management of their renal failure.

Background. Dialysis is an invasive treatment, and for some older patients, there is an associated treatment burden of dialysis-related symptoms. An alternative choice is conservative management, but little is known about those who make this decision and how they are supported through the process.

Design. Qualitative practitioner research study.

Method. Data were generated from nine patients' naturally occurring clinic consultations with a renal clinical nurse specialist between May 2010 - July 2010. Interviews were transcribed verbatim and findings fed back at three multi-disciplinary meetings to check for relevance and resonance. Common themes were identified and codes applied.

Results. Patients reported age and having to travel three times a week to hospital for dialysis as reasons not to opt for treatment. Others felt well without dialysis not wanting to upset the 'status quo' or to burden loved ones. Most felt equipped to make the decision following explanation and discussion with the clinical nurse specialist in the renal clinic.

Conclusions. Patients opting for conservative management give numerous reasons for this including old age, travel limitations, feeling well without dialysis and not wanting to be a burden, but appear content with their decision. One-to-one discussions with the clinical nurse specialist appear helpful during the decision-making process presenting an opportunity for advancing nursing roles in the chronic kidney disease service.

Relevance to clinical practice. Understanding patients' reasons for refusing dialysis assists in supporting until death. There is an opportunity for developing nursing practice to meet the multi-faceted needs of this group.

Referral to an Extracorporeal Membrane Oxygenation Center and Mortality Among Patients With Severe 2009 Influenza A(H1N1)

Context Extracorporeal membrane oxygenation (ECMO) can support gas exchange in patients with severe acute respiratory distress syndrome (ARDS), but its role has remained controversial. ECMO was used to treat patients with ARDS during the 2009 influenza A(H1N1) pandemic.

Electron-impact excitation of Fe II

We report in this paper the computation of accurate total collision strengths and effective collision strengths for electron-impact excitation of FeII, using the parallel R-matrix program PRMAT. Target states corresponding to the 3d(6)4s, 3d(7), 3d(6)4p and 3d(5)4s4s basis configurations were included in the calculations giving rise to a 113 LS state 354 coupled channel problem. Following a detailed systematic study of correlation effects in both the target state and collision wavefunctions, it was found that an additional 21 configuration functions needed to be included in the Configuration Interaction expansion to obtain significantly more accurate target states and collision wavefunctions. This much improved 26-configuration model has been used to calculate converged total effective collision strengths for all sextet to quartet transitions among these levels with total spin S=2, giving a total of 1785 lines. These calculations have laid the foundation for an approach which may be adopted in the study of electron collisions with the low ionization stages of other iron peak elements. The work has been further extended with the commencement of a Breit-Pauli relativistic calculation for one of the smaller models and includes 262 fine-structure levels and over 1800 coupled channels. At the same time the PRMAT parallel R-matrix package is being extended to include relativistic effects which will allow us to attempt the more sophisticated 26-configuration model and produce for the first time the amount and quality of atomic data required to perform a meaningful synthesis of the Fe II spectrum.

Chemical structural effects on γ-ray spectra of positron annihilation in fluorobenzenes

Spectra of ?-ray Doppler shifts for positron annihilation in benzene and its fluoro-derivatives are simulated using low energy plane wave positron (LEPWP) approximation. The results are compared with available measurements. It is found that the Doppler shifts in these larger aromatic compounds are dominated by the contributions of the valence electrons and that the LEPWP model overestimates the measurements by approximately 30%, in agreement with previous findings in noble gases and small molecules. It is further revealed that the halogen atoms not only switch the sign of the charges on carbon atoms that they bond to, but that they also polarize other C-H bonds in the molecule leading to a redistribution of the molecular electrostatic potentials. As a result, it is likely that the halogen atoms contribute more significantly to the annihilation process. The present study also suggests that, while the Doppler shifts are sensitive to the number of valence electrons in the molecules, they are less sensitive to the chemical structures of isomers that have the same numbers and type of atoms and, hence, the same numbers of electrons. Further investigation of this effect is warranted. © EDP Sciences, Società Italiana di Fisica, Springer-Verlag 2012.

R-matrix-Floquet theory of multiphoton processes:VIII. A linear equations method

A new linear equations method for calculating the R-matrix, which arises in the R-matrix-Floquet theory of multiphoton processes, is introduced. This method replaces the diagonalization of the Floquet Hamiltonian matrix by the solution of a set of linear simultaneous equations which are solved, in the present work, by the conjugate gradient method. This approach uses considerably less computer memory and can be readily ported onto parallel computers. It will thus enable much larger problems of current interest to be treated. This new method is tested by applying it to three-photon ionization of helium at frequencies where double resonances with a bound state and autoionizing states are important. Finally, an alternative linear equations method, which avoids the explicit calculation of the R-matrix by incorporating the boundary conditions directly, is described in an appendix.