Understanding Grafted Cations in Controlled Environments for Heterogeneous Catalysis

Catalytic processes occurring on the surfaces of heterogeneous catalysts are controlled by the molecular structures of active sites where these reactions occur. These active sites can be broadly thought to consist of an active center, where bond making and breaking events occur, surrounding by the surface of the support. These are the inner-sphere (i.e. active center) and outer-sphere (i.e. surface) environments of the active site. Catalyst design typically focuses on the choice of the optimal inner-sphere environment, while surfaces are often regarded as inert oxide supports onto which active sites are dispersed to facilitate catalyst recovery. In this thesis, I demonstrate that the outer-sphere surface environment is, in fact, an essential element for controlling the structure and reactivity of active sites supported on silicates.The theoretical concepts, silicate supports, and synthetic approaches that are used in this thesis are introduced in Chapter 1. Given the importance of silanol groups as grafting sites in synthetic approaches used in this thesis, I begin by providing a detailed study of silanol speciation across zeotypes and amorphous supports, in Chapter 2. Subsequently, I provide an example of how silanol environments control grafting processes and how crystalline silicates provide stable support environments for FeIII cations, in Chapter 3. I then introduce an approach to synthesizing well-defined active sites by controlling the structure of a grafted cation using an organic ligand, applied to calix[4]arene-TiIV complexes grafted on amorphous SiO2 as epoxidation catalysts, in Chapter 4. Having established the structure of silicates and approaches to synthesize well-defined active sites on their surface, I present three studies where this enables the study of structure and catalytic properties. In Chapter 5, I demonstrate how this approach enables the unambiguous deconvolution of the effect of support outer-sphere on epoxidation catalysis. In Chapter 6, I investigate how the support outer-sphere can also control the conformation and structure of grafted complexes, while providing insight into adsorption processes occurring on surfaces. Finally, in Chapter 7, I provide a detailed mechanistic study of how partially confining outer-sphere environments impact catalytic reactivity for olefin epoxidation. Taken together, this work provides fresh insights into the structure of silicate supports and their ability to control catalysis, providing an additional and important avenue to the design of heterogeneous catalysts

Holographic thermalization of charged operators

We study a light-like charged collapsing shell in AdS-Reissner-Nordstrom spacetime, investigating whether the corresponding Vaidya metric is supported by matter that satisfies the null energy condition. We find that, if the absolute value of the charge decreases during the collapse, energy conditions are fulfilled everywhere in spacetime. On the other hand, if the absolute value of the charge increases, the metric does not satisfy energy conditions in the IR region. Therefore, from the gauge/gravity perspective, this last case is only useful to study the thermalization of the UV degrees of freedom. For all these geometries, we probe the thermalization process with two point correlators of charged operators, finding that the thermalization time grows with the charge of the operator, as well as with the dimension of space.Comment: 28 pages, 19 figure

Towards Robust Velocity and Position Estimation of Opponents for Autonomous Racing Using Low-Power Radar

This paper presents the design and development of an intelligent subsystem that includes a novel low-power radar sensor integrated into an autonomous racing perception pipeline to robustly estimate the position and velocity of dynamic obstacles. The proposed system, based on the Infineon BGT60TR13D radar, is evaluated in a real-world scenario with scaled race cars. The paper explores the benefits and limitations of using such a sensor subsystem and draws conclusions based on field-collected data. The results demonstrate a tracking error up to 0.21 +- 0.29 m in distance estimation and 0.39 +- 0.19 m/s in velocity estimation, despite the power consumption in the range of 10s of milliwatts. The presented system provides complementary information to other sensors such as LiDAR and camera, and can be used in a wide range of applications beyond autonomous racing

Chaos detection tools: application to a self-consistent triaxial model

Together with the variational indicators of chaos, the spectral analysis methods have also achieved great popularity in the field of chaos detection. The former are based on the concept of local exponential divergence. The latter are based on the numerical analysis of some particular quantities of a single orbit, e.g. its frequency. In spite of having totally different conceptual bases, they are used for the very same goals such as, for instance, separating the chaotic and the regular component. In fact, we show herein that the variational indicators serve to distinguish both components of a Hamiltonian system in a more reliable fashion than a spectral analysis method does. We study two start spaces for different energy levels of a self?consistent triaxial stellar dynamical model by means of some selected variational indicators and a spectral analysis method. In order to select the appropriate tools for this paper, we extend previous studies where we make a comparison of several variational indicators on different scenarios. Herein, we compare the Average Power Law Exponent (APLE) and an alternative quantity given by the Mean Exponential Growth factor of Neary Orbits (MEGNO): the MEGNO?s Slope Estimation of the largest Lyapunov Characteristic Exponent (SElLCE). The spectral analysis method selected for the investigation is the Frequency Modified Fourier Transform (FMFT). Besides a comparative study of the APLE, the Fast Lyapunov Indicator (FLI), the Orthogonal Fast Lyapunov Indicator (OFLI) and the MEGNO/SElLCE, we show that the SElLCE could be an appropriate alternative to the MEGNO when studying large samples of initial conditions. The SElLCE separates the chaotic and the regular components reliably and identifies the different levels of chaoticity. We show that the FMFT is not as reliable as the SElLCE to describe clearly the chaotic domains in the experiments. We use the latter indicator as the main variational indicator to analyse the phase space portraits of the model under study.Fil: Maffione, Nicolas Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Instituto de Astrofísica de La Plata; Argentina. Universidad Nacional de la Plata. Facultad de Ciencias Astronómicas y Geofísicas; ArgentinaFil: Darriba, Luciano Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Instituto de Astrofísica de La Plata; Argentina. Universidad Nacional de la Plata. Facultad de Ciencias Astronómicas y Geofísicas; ArgentinaFil: Cincotta, Pablo Miguel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Instituto de Astrofísica de La Plata; Argentina. Universidad Nacional de la Plata. Facultad de Ciencias Astronómicas y Geofísicas; ArgentinaFil: Giordano, Claudia Marcela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Instituto de Astrofísica de La Plata; Argentina. Universidad Nacional de la Plata. Facultad de Ciencias Astronómicas y Geofísicas; Argentin

Climatic control on stacking and connectivity of fluvial successions: Upper Cretaceous Bajo Barreal Formation of the Golfo San Jorge basin, Patagonia

Climate impact on alluvial organization owing to its control on water availability and sediment delivery within the catchment, but temporal changes in stacking patterns are often interpreted to reflect changes in subsidence and base level. To test for evidence of climatic control on the stacking pattern, we study an outcrop succession with two styles of stacking within the Upper Cretaceous Bajo Barreal Formation in the Cerro Ballena anticline, Golfo San Jorge Basin, Argentina. The 385 m thick and 2.5 km wide exposure has layer-cake geometry, lacking either large-scale erosional surfaces, fluvial terraces, or evident paleosols, dismissing either local tectonic activity or base-levels shifts. Rooted in a paleohydrological study recognizing upward increasing in both channel width and flow depth of formative rivers, we use spectral gamma-ray logs, x-ray diffraction in mudstones, and sandstone petrography to understand the controls on the stacking pattern. At the base, Section A consists of small-scale, isolated channels fills in a siliciclastic floodplain with sand:mud ratio of ~1:6, whereas the overlying Section B has a sand-mud ratio of ~1:3, with larger-scale channels and greater inter-connectivity within a volcaniclastic floodplain. Upward reduction in K percentage through Section A parallel with increasing kaolinite content, and mudstone samples from Section B contains a higher proportion of kaolinite than Section A samples, evidencing an upward increase in paleo-weathering in humid conditions. Detrital components of Section A indicate several volcanic sources (e.g., basic-intermediate components derived from the Middle Jurassic Bahía Laura Group and acidic components sourced from the Andes Cordillera), whereas Section B exclusively contains acidic clasts derived from the Andes Cordillera. Simultaneous changes in detrital constituents, suspended load type, and increasing scale of the rivers in Section B occur coeval with increases in channel inter-connectivity, here related to the increase of river discharge and sediment supply in a humid climate, favoring more frequent avulsions or higher channel migration rates in a relatively flat geomorphic scenario. The study demonstrates, combining independent lines of evidence, that climate change can impact the stacking and connectivity of potential sandstone reservoirs.Fil: Paredes, José Matildo. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de la Patagonia "San Juan Bosco"; ArgentinaFil: Giordano, Sergio Roberto. No especifíca;Fil: Olazábal, Sabrina Ximena. Universidad Nacional de la Patagonia "San Juan Bosco"; ArgentinaFil: Valle, Mauro Nicolás. Universidad Nacional de la Patagonia "San Juan Bosco"; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Allard, José Oscar. Universidad Nacional de la Patagonia "San Juan Bosco"; ArgentinaFil: Foix, Nicolas. Universidad Nacional de la Patagonia "San Juan Bosco"; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Tunik, Maisa Andrea. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte. Instituto de Investigación en Paleobiología y Geología; Argentin

Temperature-Driven Developmental Modulation of Yield Response to Nitrogen in Wheat and Maize

Nitrogen management is central to the economic and environmental dimensions of agricultural sustainability. Yield response to nitrogen fertilisation results from multiple interacting factors. Theoretical frameworks are lagging for the interaction between nitrogen and air temperature, the focus of this study. We analyse the relation between yield response to nitrogen fertiliser and air temperature in the critical period of yield formation for spring wheat in Australia, winter wheat in the US, and maize in both the US and Argentina. Our framework assumes (i) yield response to nitrogen fertiliser is primarily related to grain number per m2, (ii) grain number is a function of three traits: the duration of the critical period, growth rate during the critical period, and reproductive allocation, and (iii) all three traits vary non-linearly with temperature. We show that “high” nitrogen supply may be positive, neutral, or negative for yield under “high” temperature, depending on the part of the response curve captured experimentally. The relationship between yield response to nitrogen and mean temperature in the critical period was strong in wheat and weak in maize. Negative associations for both spring wheat in Australia and winter wheat with low initial soil nitrogen ( 120 kg N ha-1) that favoured grain number and compromised grain fill, the relation between yield response to nitrogen and temperature was positive for winter wheat. The framework is particularly insightful where data did not match predictions; a non-linear function integrating development, carbon assimilation and reproductive partitioning bounded the pooled data for maize in the US and Argentina, where water regime, previous crop, and soil nitrogen overrode the effect of temperature on yield response to nitrogen fertilisation.Fil: Sadras, Victor O.. University of Adelaide; Australia. South Australian Research And Development Institute; AustraliaFil: Giordano, Nicolas. Kansas State University; Estados UnidosFil: Correndo, Adrian. Kansas State University; Estados UnidosFil: Cossani, C. Mariano. University of Adelaide; Australia. South Australian Research And Development Institute; AustraliaFil: Ferreyra, Juan M.. No especifíca;Fil: Caviglia, Octavio Pedro. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de Entre Ríos; ArgentinaFil: Coulter, Jeffrey A.. University of Minnesota; Estados UnidosFil: Ciampitti, Ignacio Antonio. Kansas State University; Estados UnidosFil: Lollato, Romulo P.. Kansas State University; Estados Unido

Magnetic particle embedded in a piezoelectric matrix: analysis and applications

We take into consideration a nonlinear magnetostrictive particle embedded in a piezoelectric matrix in order to obtain (stress mediated) magneto-electric effects with applications to memory cells. The micromechanical analysis is conducted through the magneto-electro-elastic Eshelby tensor in an anisotropic environment. The results show the equilibrium orientations of magnetization versus the applied fields and the boundary conditions. In particular, a bi-stable behaviour (controlled by the applied electric field) can be obtained and it could be useful for applications to memory cells design