Perspective Outlook on Operando Photoelectron and Absorption Spectroscopy to Probe Catalysts at the Solid Liquid Electrochemical Interface

Operando X-ray Photoelectron and Absorption Spectroscopy (XPS and XAS) using soft (up to 2 KeV) and tender (2–10 KeV) X-rays applied to study functional materials for energy conversion has gone through great development in the last years and several approaches to different cell designs combined with instrumentation development now allow successful characterization of electrode-electrolyte interfaces under working conditions. An overview of the current state and challenges are presented along with an outlook into the direction that future development should take, which we expect would allow us to expand and complete our understanding of the liquid-solid electrochemical interfaces

Study of errors in the integration of the two-body problem using generalized Sundman's anomalies

[EN] As is well known, the numerical integration of the two body problem with constant step presents problems depending on the type of coordinates chosen. It is usual that errors in Runge-Lenz's vector cause an artificial and secular precession of the periaster although the form remains symplectic, theoretically, even when using symplectic methods. Provided that it is impossible to preserve the exact form and all the constants of the problem using a numerical method, a possible option is to make a change in the variable of integration, enabling the errors in the position of the periaster and in the speed in the apoaster to be minimized for any eccentricity value between 0 and 1. The present work considers this casuistry. We provide the errors in norm infinite, of different quantities such as the Energy, the module of the Angular Moment vector and the components of Runge-Lenz's vector, for a large enough number of orbital revolutions.Lopez Orti, JA.; Marco Castillo, FJ.; Martínez Uso, MJ. (2014). Study of errors in the integration of the two-body problem using generalized Sundman's anomalies. SEMA SIMAI Springer Series. 4:105-112. doi:10.1007/978-3-319-06953-1_11S1051124Brower, D., Clemence, G.M.: Celestial Mechanics. Academic, New York (1965)Brumberg, E.V.: Length of arc as independent argument for highly eccentric orbits. Celest. Mech. 53, 323–328 (1992)Fehlberg, E., Marsall, G.C.: Classical fifth, sixth, seventh and eighth Runge–Kutta formulas with stepsize control. Technical report, NASA, R-287 (1968)Ferrándiz, J.M., Ferrer, S., Sein-Echaluce, M.L.: Generalized elliptic anomalies. Celest. Mech. 40, 315–328 (1987)Gragg, W.B.: Repeated extrapolation to the limit in the numerical solution of ordinary differential equations. SIAM J. Numer. Anal. 2, 384–403 (1965)Janin, G.: Accurate computation of highly eccentric satellite orbits. Celest. Mech. 10, 451–467 (1974)Janin, G., Bond, V.R.: The elliptic anomaly. Technical memorandum, NASA, n. 58228 (1980)Levallois, J.J., Kovalevsky, J.: Géodésie Générale, vol. 4. Eyrolles, Paris (1971)López, J.A., Agost, V., Barreda, M.: A note on the use of the generalized Sundman transformations as temporal variables in celestial mechanics. Int. J. Comput. Math. 89, 433–442 (2012)López, J.A., Marco, F.J., Martínez, M.J.: A study about the integration of the elliptical orbital motion based on a special one-parametric family of anomalies. Abstr. Appl. Anal. 2014, ID 162060, 1–11 (2014)Nacozy, P.: The intermediate anomaly. Celest. Mech. 16, 309–313 (1977)Sundman, K.: Memoire sur le probleme des trois corps. Acta Math. 36, 105–179 (1912)Tisserand, F.F.: Traité de Mecanique Celeste. Gauthier-Villars, Paris (1896)Velez, C.E., Hilinski, S.: Time transformation and Cowell’s method. Celest. Mech. 17, 83–99 (1978

On the operando structure of ruthenium oxides during the oxygen evolution reaction in acidic media

In the search for rational design strategies for oxygenevolutionreaction (OER) catalysts, linking the catalyst structure to activityand stability is key. However, highly active catalysts such as IrO x and RuO x undergostructural changes under OER conditions, and hence, structure-activity-stabilityrelationships need to take into account the operando structure ofthe catalyst. Under the highly anodic conditions of the oxygen evolutionreaction (OER), electrocatalysts are often converted into an activeform. Here, we studied this activation for amorphous and crystallineruthenium oxide using X-ray absorption spectroscopy (XAS) and electrochemicalscanning electron microscopy (EC-SEM). We tracked the evolution ofsurface oxygen species in ruthenium oxides while in parallel mappingthe oxidation state of the Ru atoms to draw a complete picture ofthe oxidation events that lead to the OER active structure. Our datashow that a large fraction of the OH groups in the oxide are deprotonatedunder OER conditions, leading to a highly oxidized active material.The oxidation is centered not only on the Ru atoms but also on theoxygen lattice. This oxygen lattice activation is particularly strongfor amorphous RuO x . We propose that thisproperty is key for the high activity and low stability observed foramorphous ruthenium oxide.Catalysis and Surface Chemistr

Detecting a stochastic gravitational wave background with the Laser Interferometer Space Antenna

The random superposition of many weak sources will produce a stochastic background of gravitational waves that may dominate the response of the LISA (Laser Interferometer Space Antenna) gravitational wave observatory. Unless something can be done to distinguish between a stochastic background and detector noise, the two will combine to form an effective noise floor for the detector. Two methods have been proposed to solve this problem. The first is to cross-correlate the output of two independent interferometers. The second is an ingenious scheme for monitoring the instrument noise by operating LISA as a Sagnac interferometer. Here we derive the optimal orbital alignment for cross-correlating a pair of LISA detectors, and provide the first analytic derivation of the Sagnac sensitivity curve.Comment: 9 pages, 11 figures. Significant changes to the noise estimate

Uncoupling the structure–activity relationships of β2 adrenergic receptor ligands from membrane binding

Ligand binding to membrane proteins may be significantly influenced by the interaction of ligands with the membrane. In particular, the microscopic ligand concentration within the membrane surface solvation layer may exceed that in bulk solvent, resulting in overestimation of the intrinsic protein−ligand binding contribution to the apparent/measured affinity. Using published binding data for a set of small molecules with the β2 adrenergic receptor, we demonstrate that deconvolution of membrane and protein binding contributions allows for improved structure−activity relationship analysis and structure-based drug design. Molecular dynamics simulations of ligand bound membrane protein complexes were used to validate binding poses, allowing analysis of key interactions and binding site solvation to develop structure−activity relationships of β2 ligand binding. The resulting relationships are consistent with intrinsic binding affinity (corrected for membrane interaction). The successful structure-based design of ligands targeting membrane proteins may require an assessment of membrane affinity to uncouple protein binding from membrane interactions

CMOS-compatible nanoscale gas-sensor based on field effect

The integration of a solid state gas sensor of the metal oxide sensor type into CMOS technology still is a challenge because of the high temperatures during metal oxide annealing and sensor operation that do not comply with silicon device stability. In the presence of an external electric field sensor sensitivity can be controlled through a change of the Fermi energy level and consequently it is possible to reduce the operation temperature. Based in this effect, a novel field effect gas sensor was developed resembling a reversed insulated gate field effect transistor (IGFET) with the thickness of gas sensing layer in the range of the Debye length (L-D). Under these conditions the controlling electrical field reaches the sensitive surface and a modulation of the Fermi energy level occurs, producing an effective control of gas sensitivity and sensor response. In this paper several aspects are treated, like technological fabrication process, complete sensor characterization by means of an electrical model and sensor response measurements. Other effects as base-line drift effects and layer thickness implications also are studied

Probing Operating Electrochemical Interfaces by Photons and Neutrons

The operation of all electrochemical energy-related systems, such as supercapacitors, batteries, fuel cells, etc. depends largely on the processes occurring at electrochemical interfaces at which charge separation and chemical reactions occur. Evolution of structure and composition at the interface between electrodes and electrolytes affects all the device′s functional parameters including power and long-term performance stability. The analytical techniques capable of exploring the interfaces are still very limited, and more often only ex situ studies are performed. This sometimes leads to a loss of important pieces of the puzzle, hindering the development of novel technologies, as in many cases intermediates and electrochemical reaction products cannot be “quenched” for post-process analyses. Techniques capable of operando probing of electrochemical interfaces by photons and neutrons have become an extensively growing field of research. This review aims at highlighting approaches and developing ideas on the adaptation of photoelectron, X-ray absorption, vibrational spectroscopy, nuclear magnetic resonance, and X-ray and neutron reflectometry in electrochemical studies

CMOS-compatible field effect nanoscale gas-sensor: Operation and annealing models

Complete modelling of electrically controlled nanoscale gas sensors with Poisson, Wolkenstein, Fokker-Planck and continuity is presented. Based on a plausible Drift explanation we developed suitable models for sensitivity control and operational modes. An onset for CMOS-complying annealing procedures is given