Dispersion forces drive water oxidation in molecular ruthenium catalysts

Rational design of artificial water-splitting catalysts is central for developing new sustainable energy technology. However, the catalytic efficiency of the natural light-driven water-splitting enzyme, photosystem II, has been remarkably difficult to achieve artificially. Here we study the molecular mechanism of ruthenium-based molecular catalysts by integrating quantum chemical calculations with inorganic synthesis and functional studies. By employing correlatedab initiocalculations, we show that the thermodynamic driving force for the catalysis is obtained by modulation of π-stacking dispersion interactions within the catalytically active dimer core, supporting recently suggested mechanistic principles of Ru-based water-splitting catalysts. The dioxygen bond forms in a semi-concerted radical coupling mechanism, similar to the suggested water-splitting mechanism in photosystem II. By rationally tuning the dispersion effects, we design a new catalyst with a low activation barrier for the water-splitting. The catalytic principles are probed by synthesis, structural, and electrochemical characterization of the new catalyst, supporting enhanced water-splitting activity under the examined conditions. Our combined findings show that modulation of dispersive interactions provides a rational catalyst design principle for controlling challenging chemistries. © The Royal Society of Chemistry 2020.Peer reviewe

Enhanced thermal stability and fracture toughness of TiAlN coatings by Cr, Nb and V-alloying

The effect of metal alloying on mechanical properties including hardness and fracture toughness were investigated in three alloys, Ti~0.33Al0.50(Me)~0.17N (Me¿=¿Cr, Nb and V), and compared to Ti0.50Al0.50N, in the as-deposited state and after annealing. All studied alloys display similar as-deposited hardness while the hardness evolution during annealing is found to be connected to phase transformations, related to the alloy's thermal stability. The most pronounced hardening was observed in Ti0.50Al0.50N, while all the coatings with additional metal elements sustain their hardness better and they are harder than Ti0.50Al0.50N after annealing at 1100¿°C. Fracture toughness properties were extracted from scratch tests. In all tested conditions, as-deposited and annealed at 900 and 1100¿°C, Ti0.33Al0.50Nb0.17N show the least surface and sub-surface damage when scratched despite the differences in decomposition behavior and h-AlN formation. Theoretically estimated ductility of phases existing in the coatings correlates well with their crack resistance. In summary, Ti0.33Al0.50Nb0.17N is the toughest alloy in both as-deposited and post-annealed states.Peer ReviewedPostprint (author's final draft

Mechanical strength of ground WC-Co cemented carbides after coating deposition

Manufacturing of hardmetal tools often involves surface grinding, ion etching and final coating. Each stage throughout the manufacturing chain introduces surface integrity changes which may be critical for defining the final mechanical behavior of the coated tools. Within this context, an experimental test program has been developed to assess the influence of a coating (TiN) deposition on surface integrity and transverse rupture strength of a previously ground fine-grained WC-Co grade substrate. Four different substrate surface finish conditions (prior to ion etching and coating) were evaluated: as sintered (AS), ground (G), polished (P), and ground plus high temperature annealing (GTT). Surface integrity and fracture resistance characterization, complemented with a detailed fractographic analysis, were performed on both uncoated and coated samples. Results show that the surface integrity after grinding has been partly modified during the ion etching and film deposition processes, particularly in terms of a reduced compressive residual stress state at the substrate surface level. Consequently, the grinding induced strength enhancement in hardmetals is reduced for coated specimens. Main reason behind it is the change of nature, location and stress state acting on critical flaw: from processing defects existing at the subsurface (uncoated G specimens) to grinding-induced microcracks located close to the interface between coating and substrate, but within the subsurface of the latter (coated G specimens). This is not the case for AS and P conditions, where flexural strength does not change as a result of ion etching and coating. Finally, fracture resistance increases slightly for GTT specimens after coating process, possibly caused by a beneficial effect of the deposited film on the residual stress state at the surface.Preprin

Mechanical strength of ground WC-Co cemented carbides after coating deposition

Manufacturing of hardmetal tools often involves surface grinding, ion etching and final coating. Each stage throughout the manufacturing chain introduces surface integrity changes which may be critical for defining the final mechanical behavior of the coated tools. Within this context, an experimental test program has been developed to assess the influence of a coating (TiN) deposition on surface integrity and transverse rupture strength of a previously ground fine-grained WC-Co grade substrate. Four different substrate surface finish conditions (prior to ion etching and coating) were evaluated: as sintered (AS), ground (G), polished (P), and ground plus high temperature annealing (GTT). Surface integrity and fracture resistance characterization, complemented with a detailed fractographic analysis, were performed on both uncoated and coated samples. Results show that the surface integrity after grinding has been partly modified during the ion etching and film deposition processes, particularly in terms of a reduced compressive residual stress state at the substrate surface level. Consequently, the grinding induced strength enhancement in hardmetals is reduced for coated specimens. Main reason behind it is the change of nature, location and stress state acting on critical flaw: from processing defects existing at the subsurface (uncoated G specimens) to grinding-induced microcracks located close to the interface between coating and substrate, but within the subsurface of the latter (coated G specimens). This is not the case for AS and P conditions, where flexural strength does not change as a result of ion etching and coating. Finally, fracture resistance increases slightly for GTT specimens after coating process, possibly caused by a beneficial effect of the deposited film on the residual stress state at the surfac

Dynamical study on polaron formation in a metal/polymer/metal structure

By considering a metal/polymer/metal structure within a tight-binding one-dimensional model, we have investigated the polaron formation in the presence of an electric field. When a sufficient voltage bias is applied to one of the metal electrodes, an electron is injected into the polymer chain, then a self-trapped polaron is formed at a few hundreds of femtoseconds while it moves slowly under a weak electric field (not larger than $$ V/cm). At an electric field between $1.0\times 10^4$ V/cm and $$ V/cm, the polaron is still formed, since the injected electron is bounded between the interface barriers for quite a long time. It is shown that the electric field applied at the polymer chain reduces effectively the potential barrier in the metal/polymer interface

Amounts of litter fall in some pine forests in a European transect, in particular Scots pine.

Pine litter fall data, mainly needle litter, were available for 64 plots in a transect from the Arctic Circle in Fennoscandia (41 plots) to southern Spain (22 further plots in continental Europe) and one in the American Midwest). Data originated from a total of eight pine species. Regressions were calculated mainly for needle litter fall and to some extent for total litter fall. We obtained a highly significant linear relationship for needle litter fall and latitude (R 2adj = 0.285; n = 58; P < 0.001) when using needle litter fall data from all pine species. Combining sites in the boreal and Atlantic climates gave an R2 adj of 0.732 with n = 45 (P < 0.001). A multiple linear relationship using stand age, latitude and basal area was highly significant and gave an R2adj value of 0.412 (n = 54; P < 0.001). For the amount of Scots pine needle litter in Fennoscandia, the best simple linear relationships were obtained with site index (H 100) (R2 adj = 0.349), latitude (R2adj = 0.331) and basal area (R2adj = 0.324) as predictor variables, whereas the regressions on altitude and stand age were significant only with P < 0.01. An X2 function for stand age improved the relationship with age to R2adj = 0.243. Multiple regression relationships for Fennoscandia between needle litter fall and latitude plus basal area and that to latitude plus basal area plus age were highly significant (R2adj = 0.605 and 0.661, respectively, with n = 41). In a stepwise procedure using data from the same sites, combinations of the factors latitude, site index, basal area and stand age could explain as much as 78 % of the needle litter fall. For total litter fall as measured by the same method as needle litter we related data from 32 sites to that of needle litter fall and obtained highly significant relationships indicating that needle litter fall may be used as an index for total litter fall. © 1999 Inra/Éditions scientifiques et médicales Elsevier SAS.Chute de litière dans quelques forêts de pins, en particulier du Pin sylvestre, le long d'un transect européen. Les données de chute de litière, essentiellement des chutes d'aiguilles, étaient disponibles pour 64 sites le long d'un transect depuis le cercle polaire en Scandinavie (41 sites) jusqu'au Sud de l'Espagne (22 sites supplémentaires en Europe continentale) et un site dans le midouest américain. Les données proviennent de huit espèces de Pin. Des régressions ont été calculées principalement pour la chute d'aiguilles et dans certains cas pour la chute totale de litière. Il existe une relation linéaire hautement significative entre la chute des aiguilles et la latitude (R2adj = 0.285 ; n = 58; p < 0,001) lorsque l'ensemble des données pour toutes les espèces sont utilisées. La combinaisons des sites en climat boréal et atlantique donne un R2adj de 0.732 pour n = 45 (p < 0,001). Une relation linéaire multiple, utilisant l'âge du peuplement, la latitude et la surface terrière est hautement significative et donne un R 2∼ de 0.412 (n = 54; p < 0.001). La meilleure relation linéaire, pour les retours d'aiguilles chez le Pin sylvestre en Scandinavie a été obtenue en utilisant comme variables prédictives l'indice de fertilité stationnelle « H 100 » (R2 adj = 0.349), la latitude (Radj = 0331), et la surface terrière (R2adj = 0.324 ; alors que la régression sur les variables altitudes et âge des peuplements n'était significative seulement à p < 0,01. Une fonction X2 pour l'âge du peuplement améliore la relation avec l'âge, R2adj = 0,243. Les relations multiples entre la chute des aiguilles et la latitude associée à la surface terrière et celle associée à la surface terrière plus l'âge, pour les sites Scandinaves, sont hautement significatives (R2 adj = 0,605 et R2adj = 0,661, respectivement, avec n = 41 ). La procédure de régression progressive sur les données des mêmes sites, combinaisons des variables latitude, indice de fertilité, surface terrière et âge du peuplement permet d'expliquer 78 % de la variation de la chute des aiguilles. Des relations hautement significatives ont été calculées sur les données des retours totaux de litière, utilisant la même méthodologie sur 32 des sites. Elles démontrent que la quantité des chutes des seules aiguilles peut être utilisée comme indice pour la chute totale de la litière. © 1999 Inra/Éditions scientifiques et médicales Elsevier SAS

Contact damage resistance of TiN-coated hardmetals: Beneficial effects associated with substrate grinding

Contact loading is a common service condition for coated hardmetal tools and components. Substrate grinding represents a key step within the manufacturing chain of these coated systems. Within this context, the influence of surface integrity changes caused by abrasive grinding of the hardmetal substrate, prior to coating, is evaluated with respect to contact damage resistance. Three different substrate surface finish conditions are studied: ground (G), mirror-like polished (P) and ground plus heat-treated (GTT). Tests are conducted by means of spherical indentation under increasing monotonic load and the contact damage resistance is assessed. Substrate grinding enhances resistance against both crack nucleation at the coating surface and subsequent propagation into the hardmetal substrate. Hence, crack emergence and damage evolution is effectively delayed for the coated G condition, as compared to the reference P one. The observed system response is discussed on the basis of the beneficial effects associated with compressive residual stresses remnant at the subsurface level after grinding, ion-etching and coating. The influence of the stress state is further corroborated by the lower contact damage resistance exhibited by the coated GTT specimens. Finally, differences observed on the interaction between indentation-induced damage and failure mode under flexural testing points in the direction that substrate grinding also enhances damage tolerance of the coated system when exposed to contact loadsPeer ReviewedPostprint (author's final draft

Genomic Deletion Marking an Emerging Subclone of Francisella tularensis subsp. holarctica in France and the Iberian Peninsula

P. 7465-7470Francisella tularensis subsp. holarctica is widely disseminated in North America and the boreal and temperate regions of the Eurasian continent. Comparative genomic analyses identified a 1.59-kb genomic deletion specific to F. tularensis subsp. holarctica isolates from Spain and France. Phylogenetic analysis of strains carrying this deletion by multiple-locus variable-number tandem repeat analysis showed that the strains comprise a highly related set of genotypes, implying that these strains were recently introduced or recently emerged by clonal expansion in France and the Iberian PeninsulaS

Quasiclassical description of transport through superconducting contacts

We present a theoretical study of transport properties through superconducting contacts based on a new formulation of boundary conditions that mimics interfaces for the quasiclassical theory of superconductivity. These boundary conditions are based on a description of an interface in terms of a simple Hamiltonian. We show how this Hamiltonian description is incorporated into quasiclassical theory via a T-matrix equation by integrating out irrelevant energy scales right at the onset. The resulting boundary conditions reproduce results obtained by conventional quasiclassical boundary conditions, or by boundary conditions based on the scattering approach. This formalism is well suited for the analysis of magnetically active interfaces as well as for calculating time-dependent properties such as the current-voltage characteristics or as current fluctuations in junctions with arbitrary transmission and bias voltage. This approach is illustrated with the calculation of Josephson currents through a variety of superconducting junctions ranging from conventional to d-wave superconductors, and to the analysis of supercurrent through a ferromagnetic nanoparticle. The calculation of the current-voltage characteristics and of noise is applied to the case of a contact between two d-wave superconductors. In particular, we discuss the use of shot noise for the measurement of charge transferred in a multiple Andreev reflection in d-wave superconductors

Coherent electron-phonon coupling and polaron-like transport in molecular wires

We present a technique to calculate the transport properties through one-dimensional models of molecular wires. The calculations include inelastic electron scattering due to electron-lattice interaction. The coupling between the electron and the lattice is crucial to determine the transport properties in one-dimensional systems subject to Peierls transition since it drives the transition itself. The electron-phonon coupling is treated as a quantum coherent process, in the sense that no random dephasing due to electron-phonon interactions is introduced in the scattering wave functions. We show that charge carrier injection, even in the tunneling regime, induces lattice distortions localized around the tunneling electron. The transport in the molecular wire is due to polaron-like propagation. We show typical examples of the lattice distortions induced by charge injection into the wire. In the tunneling regime, the electron transmission is strongly enhanced in comparison with the case of elastic scattering through the undistorted molecular wire. We also show that although lattice fluctuations modify the electron transmission through the wire, the modifications are qualitatively different from those obtained by the quantum electron-phonon inelastic scattering technique. Our results should hold in principle for other one-dimensional atomic-scale wires subject to Peierls transitions.Comment: 21 pages, 8 figures, accepted for publication in Phys. Rev. B (to appear march 2001