Volcano | EPFL Graph Search

A volcano is a rupture in the crust of a planetary-mass object, such as Earth, that allows hot lava, volcanic ash, and gases to escape from a magma chamber below the surface. On Earth, volcanoes are most often found where tectonic plates are diverging or converging, and most are found underwater. For example, a mid-ocean ridge, such as the Mid-Atlantic Ridge, has volcanoes caused by divergent tectonic plates whereas the Pacific Ring of Fire has volcanoes caused by convergent tectonic plates. Volcanoes can also form where there is stretching and thinning of the crust's plates, such as in the East African Rift and the Wells Gray-Clearwater volcanic field and Rio Grande rift in North America. Volcanism away from plate boundaries has been postulated to arise from upwelling diapirs from the core–mantle boundary, deep in the Earth. This results in hotspot volcanism, of which the Hawaiian hotspot is an example. Volcanoes are usually not created where two tectonic plates slide past one anot

Vertical distribution of the different types of aerosols in the stratosphere: Detection of solid particles and analysis of their spatial variability

Quentin Bourgeois

Stratospheric aerosols play a significant role in stratospheric chemistry. In the past, it was assumed that only liquid droplets are present in the stratosphere. Nevertheless, a few lidar measurements have shown that sudden enhancement of aerosol content in the middle stratosphere could be due to meteoritic debris. Aircraft measurements have shown that solid particles can be found in the lower stratosphere; these particles are mainly soot, but also include some interplanetary material. In order to better document the various characteristics of aerosols in the unperturbed stratosphere (i.e., free of volcanic aerosols), we have performed observations using different balloon-borne instruments (Stratospheric and Tropospheric Aerosol Counter (STAC), Spectroscopie d'Absorption Lunaire pour l'Observation des Minoritaires Ozone et NOx (SALOMON), and Micro Radiometre Ballon (MicroRADIBAL)) and also some satellite data (Global ozone monitoring by occultation of stars Envisat (GOMOS-Envisat)). These instruments allow us to obtain the number of particles in different size classes, the wavelength dependence of aerosol extinction, and the radiance of the light scattered by aerosols. Combining all the data together, it appears that significant amounts of particles are ubiquitous in the middle stratosphere, above the canonical sulfate aerosol layer. "Background'' interplanetary dusts in low concentration are likely present in the stratosphere. Above 30 km, interplanetary dust and largest grains from meteoroid disintegration dominate. Although the disintegration of meteoroids occurs in the upper stratosphere or in the mesosphere at all latitudes, these solid aerosols can be transported to the polar regions by the general circulation and can descend into the middle and lower stratosphere during winter mesospheric descents. Between about 22 km and 30 km, soot particles contribute to the population of aerosols at all latitudes. These soot, likely originating from biomass burning at all latitudes, could be injected into the lower stratosphere by the pyroconvective effect and can then reach the middle stratosphere perhaps owing to the gravitophotophoresis effect as was theoretically proposed. In the lower unperturbed stratosphere, liquid sulfate aerosols dominate, although soot particles are still present. Local horizontal and vertical enhancements of solid aerosols have sometimes been detected, although their origin is not yet determined. The presence of these solid particles can strongly bias the interpretation of in situ and remote sensing measurements when only the presence of liquid aerosols is assumed. Therefore, a new strategy of measurement will be necessary in the future to better characterize the stratospheric aerosol content free of volcanic particles.

2008

The Genesis of Molecular Volcano Plots

Michael Markus Busch, Boodsarin Sawatlon, Matthew Wodrich

For the past two decades, linear free energy scaling relationships and volcano plots have seen frequent use as computational tools that aid in understanding and predicting the catalytic behavior of heterogeneous and electrocatalysts. Based on Sabatier's principle, which states that a catalyst should bind a substrate neither too strongly nor too weakly, volcano plots provide an estimate of catalytic performance (e.g., overpotential, catalytic cycle thermodynamics/kinetics, etc.) through knowledge of a descriptor variable. By the use of linear free energy scaling relationships, the value of this descriptor is employed to estimate the relative energies of other catalytic cycle intermediates/transition states. Postprocessing of these relationships leads to a volcano curve that reveals the anticipated performance of each catalyst, with the best species appearing on or near the peak or plateau. While the origin of volcanoes is undoubtedly rooted in examining heterogeneously catalyzed reactions, only recently has this concept been transferred to the realm of homogeneous catalysis. This Account summarizes the work done by our group in implementing and refining "molecular volcano plots" for use in analyzing and predicting the behavior of homogeneous catalysts. We begin by taking the reader through the initial proof-of-principle study that transferred the model from heterogeneous to homogeneous catalysis by examining thermodynamic aspects of a Suzuki-Miyaura cross-coupling reaction. By establishing linear free energy scaling relationships and reproducing the volcano shape, we definitively showed that volcano plots are also valid for homogeneous systems. On the basis of this key finding, we further illustrate how unified pictures of C-C cross-coupling thermodynamics were created using three-dimensional molecular volcanoes. The second section highlights an important transformation from "thermodynamic" to "kinetic" volcanoes by using the descriptor variable to directly estimate transition state barriers. Taking this idea further, we demonstrate how volcanoes can be used to directly predict an experimental observable, the turnover frequency. Discussion is also provided on how different flavors of molecular volcanoes can be used to analyze aspects of homogeneous catalysis of interest to experimentalists, such as determining the product selectivity and probing the substrate scope. The third section focuses on incorporating machine learning approaches into molecular volcanoes and invoking big-data-type approaches in the analysis of catalytic behavior. Specifically, we illustrate how machine learning can be used to predict the value of the descriptor variable, which facilitates nearly instantaneous screening of thousands of catalysts. With the large amount of data created from the machine learning/volcano plot tandem, we show how the resulting database can be mined to garner an enhanced understanding of catalytic processes. Emphasis is also placed on the latest generation of augmented volcano plots, which differ fundamentally from earlier volcanoes by elimination of the use of linear free energy scaling relationships and by assessment of the similarity of the complete catalytic cycle energy profile to that for an ideal reference species that is used to discriminate catalytic performance. We conclude by examining a handful of applications of molecular volcano plots to interesting problems in homogeneous catalysis and offering thoughts on the future prospects and uses of this new set of tools.

2021

Unraveling Metal/Pincer Ligand Effects in the Catalytic Hydrogenation of Carbon Dioxide to Formate

Boodsarin Sawatlon, Matthew Wodrich

The hydrogenation of carbon dioxide to formate is an intriguing reaction from both an environmental and an energy perspective, primarily due to the prospective uses of the product as a platform chemical in numerous applications such as an organic hydrogen carrier. Although several transition-metal-based catalysts have been shown to facilitate this chemical transformation, few guidelines exist on how best to tune the catalysts in order to achieve maximum activity. Here, we use linear scaling relationships and molecular volcano plots to gauge the potential of different metal-pincer catalysts for the aforementioned reaction. Analysis of combinations of five metals (Ru, Os, Co, Rh, and Ir) and seven tridentate pincer-type ligands reveals several complexes lying near the volcano top, suggesting that these species have nearly ideal energetic profiles for facilitating the hydrogenation reaction. In particular, catalysts bearing group 9 metal centers (Ir, Rh, Co) with pi-acidic ligands provide a clear route to improving catalytic activity. Overall, these findings highlight how linear scaling relationships and molecular volcano plots provide unique insight into the underlying stereoelectronic factors that make specific metal-ligand combinations highly efficient catalysts.