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<p dir="ltr">Zeolites are microporous, crystalline aluminosilicates widely used in catalysis and separation. The substitution of Si⁴⁺ with Al³⁺ ([AlO_4/2]^-) creates a charge imbalance that can be compensated by a metal cation or complex (Mⁿ⁺) or a Brønsted acid proton (H⁺) within microporous voids and at external surfaces. Brønsted acid sites in aluminosilicates of diverse topologies have similar acid strength, but the diffusion of reactants and products can vary depending on the micropore size, tortuosity, and connectivity. The coupled effects of H⁺-site reactivity and diffusional constraints imposed by the inorganic zeolitic framework can be assessed by the diffusion parameter, which depends on the bulk proton density ([H⁺]) and the diffusion pathlength (L), derived from the Thiele modulus expression that relates reaction and diffusion rates within porous catalysts. This motivates synthetic approaches to control zeolite properties that influence diffusion and reactivity such as crystallite size and proton density. Prior synthetic methods have tried to minimize the diffusional constraints by decreasing the diffusion pathlength (L) by synthesizing zeolite crystallites at the nanometer scale or by increasing the effective diffusivity (D_e) by synthesizing hierarchical materials. However, these synthetic approaches may simultaneously influence multiple zeolite properties, such as the spatial distribution of acid sites throughout crystallites or at extracrystalline surfaces, convoluting the influence of these properties on the rates, selectivity, and deactivation of acid-catalyzed reactions.</p><p dir="ltr">Two types of spatial distribution of acid sites could be present within a zeolite. The first is the fraction at unconfined extracrystalline surfaces, and this property is often convoluted with the effect of crystallite size. Assuming acid sites are evenly distributed through the crystallite, as the crystallite size increases, the fraction of external acid sites decreases because the surface area-to-volume decreases. The second type of spatial distribution of acid sites is referred to as “zoning”—a concentration gradient of active sites from the external surface to its core, or vice versa. This type of spatial distribution of acid sites is challenging to quantify accurately. “Zoning” effects may also occur inadvertently during zeolite synthesize using conventional methods. In this work, we synthesize zeolitic materials (i.e., MFI) with controlled spatial distribution of acid sites independently of crystallite size and H⁺-site density to study their effects on propene oligomerization catalysis. A core@shell synthesis approach was used to passivate external MFI zeolite surfaces by an inert shell (Si-MFI) of short thickness relative to the size of the core crystallite. Although other passivation treatments can cause pore blockage or narrowing, transient sorption measurement showed no additional diffusional limitations were introduced by the growth of the Si-MFI shell. Propene dimerization rates (per H⁺, 503 K, 16 – 620 kPa C₃H₆) and transient behavior upon pressure step-changes persist reveal the influence of intrazeolite diffusional constraints on the Al-MFI core due to heavier oligomer products that accumulate inside micropores. On the contrary, dimerization rates did not reach a pseudo-steady-state on Al-MFI@Si-MFI and required high temperature caused by the formation of surface carbonaceous deposits in the absence of acid sites that otherwise assist in the cracking and desorption of coke precursor species. Thus, the passivation of the external surface imposes a transport limitation at the surface due to a carbonaceous layer that forms during the reaction, restricting the diffusion of products out of crystallites and shifting the selectivity towards a lighter product composition.</p><p dir="ltr">An inverted core@shell (Si-MFI@Al-MFI) material was also synthesized to investigate the effect of the spatial distribution of acid sites on the diffusion parameter, where the acid sites are preferentially located at the external surface and the core is inert (i.e. Si-MFI). The spatial distribution of acid sites was varied by growing an Al-MFI shell on a siliceous core and maintaining a similar bulk crystallite size. Mesitylene benzylation was used to quantify the fraction of external acid sites. Differences in measured propene dimerization rates (per H⁺) and product selectivity can be rationalized considering the thickness of the Al-rich shell in the core@shell material to an Al-MFI sample of similar crystallite size, evincing the dominant influence of the diffusion parameter on propene oligomerization catalytic behavior. Overall, this study demonstrated how zeolite synthetic methods can be used to isolate the effects of spatial distributions of Al from crystallite size and H⁺-site density and provide guidance for zeolite catalyst design efforts to control structural properties that influence reactions driven by coupled kinetic-transport phenomena.</p>

The purpose of this study is to foster preservation and to encourage the correct development of East 96th Street and its surrounding neighborhood. Present as-of-right zoning regulations allow extremely tall buildings to be constructed that would create walls along the street. Modification of these zoning regulations are proposed to establish a planning guide that will improve East 96th Street aesthetically, economically and socially as well as encourage developers to invest in the neighborhood. / Master of Architecture

In recent years there has been a trend towards large-scale logistics for individual members of the public, such as ride-sharing services and drone package delivery. Efficient coordination of pickups and deliveries is essential in order to keep costs and wait times down. In this thesis we present these types of problems in a more general framework, expanding applicability of our discussion to an even wider domain of problems. We present fast new al- gorithms with supporting theoretical and experimental analysis, providing certain guarantees about how close our algorithms compare to a theoretically optimal approach. / Master of Science / In recent years there has been a trend towards large-scale logistics for individual members of the public, such as ride-sharing services and drone package delivery. Efficient coordination of pickups and deliveries is essential in order to keep costs and wait times down. In this thesis we present these types of problems in a more general framework, expanding applicability of our discussion to an even wider domain of problems. We present fast new algorithms with supporting theoretical and experimental analysis, providing certain guarantees about how close our algorithms compare to a theoretically optimal approach.

Detta arbete är författat på Kungliga Tekniska Högskolan i Stockholm inom kandidatprogrammet Fastighetsutveckling med fastighetsförmedling. Undersökningen kommer att ligga som stöd för Statens Haverikommissions utredande rapport om jordskredet i Stenungsund. Den 23 september 2023 skedde ett jordskred i Stenungsunds kommun. I ett av de områden där jordskredet utlöstes antogs nyligen en detaljplan. Den aktuella detaljplanen för det utsatta området är Munkeröd 1:12 m.fl. Detaljplaneprocessen för Munkeröd 1:12 m.fl. började redan under 2008, när ett planförslag skickades in med önskan att ändra markanvändningen från närrekreationsområde till industrimark. Under detaljplaneprocessen utfördes flera utredningar med syfte att pröva markens lämplighet för industri. Det utfördes flera geotekniska undersökningar där markens lastrestriktioner ändrades under åren. Syftet med studien är att analysera detaljplaneprocessen för Munkeröd 1:12 m.fl. samt att analysera de geotekniska undersökningarna som har skett, i syfte att ta reda på vart i detaljplaneprocessen som markens lastrestriktioner har reviderats och varför. Detta har gjorts genom en litteratur- och dokumentstudie samt en rättsvetenskaplig metod. Studien visar vart i detaljplaneprocessen som lastrestriktionerna har ändrats och varför. Revideringarna har alla skett i samband med samråd och utställningen. Det har inkommit flera yttranden under detaljplanearbetets gång med synpunkter på b.la de geotekniska undersökningarna. Studien visar även vikten av noggranna och transparenta utredningar i detaljplaneprocesser, särskilt när det gäller områden med hög skredrisk. Även om de juridiska och strukturella aspekterna av planeringen följdes, påvisar denna undersökande studie att ytterligare granskning och försiktighet är nödvändig vid stora avvikelser från gällande översiktsplaner och när markanvändningen ändras betydligt. Denna slutsats understryker behovet av att framtida planer och beslut baseras på robust och aktuell information för att minimera riskerna och säkerställa hållbara och säkra markanvändningar. / This work is authored at the Royal Institute of Technology in Stockholm within the bachelor program in Property Development and Agency. The study will assist the Swedish Accident Investigation Authority's investigative report on the landslide in Stenungsund. On September 23, 2023, a landslide occurred in the municipality of Stenungsund. In one of the areas where the landslide was triggered, a detailed zoning plan was recently adopted. The current detailed zoning plan for the affected area is Munkeröd 1:12 et al. The detailed planning process for Munkeröd 1:12 et al. began as early as 2008, when a planning proposal was submitted with the desire to change the land use from a local recreation area to industrial land. Several investigations were carried out during the detailed planning process to test the suitability of the land for industry. Several geotechnical investigations were conducted where the load restrictions of the land were changed over the years. The purpose of the study is to analyze the detailed planning process for Munkeröd 1:12 et al. and to analyze the geotechnical investigations that have taken place, with purpose to find out where in the detailed planning process the land's load restrictions have been revised and why. This has been done through a literature- and document study as well as a legal scientific method. The study shows where in the detailed planning process the load restrictions have been changed and why. The revisions have all taken place in connection with consultations and exhibitions of the proposed plan. Several comments were received during the detailed planning work with views on, among other things, the geotechnical investigations. The study also shows the importance of thorough and transparent investigations in detailed planning processes, especially regarding areas with high landslide risk. Although the legal and structural aspects of planning were followed, this investigative study demonstrates that further scrutiny and caution are necessary in the case of major deviations from current comprehensive plans and when land use is significantly changed. This conclusion emphasizes the need for future plans and decisions to be based on robust and current information to minimize risks and ensure sustainable and safe land uses.

O presente trabalho tem como finalidade apresentar os resultados obtidos no Zoneamento Geotécnico Geral da Folha de Americana/SP, na escala 1:50.000, através do mapeamento geotécnico e o levantamento das características dos atributos do meio físico representados pelo substrato rochoso, material inconsolidado e landforms da área, utilizando como base a metodologia proposta pela Escola de Engenharia de São Carlos - USP (Zuquette, 1987). Como ferramenta de auxílio do trabalho foram utilizados a Técnica de Avaliação de Terreno, de acordo com Lollo (1996), e o Sistema de Informações Geográficas (SIG-Idrisi 32), que auxiliaram na otimização dos trabalhos e manipulação dos dados obtidos, resultando na geração dos documentos cartográficos de forma satisfatória. Por fim, foram elaborados os seguintes documentos cartográficos : Mapa de Documentação, Mapa de Substrato Rochoso, Carta de Declividade, Mapa de Rede de Drenagem, Mapa de Materiais Inconsolidados, Mapa de Landforms e a Carta de Zoneamento Geotécnico Geral. / This research has the proposal of presenting General Geotecnical Zoning of the square of Americana/SP with of 1:50.000 scale, considering geotechnical mapping and the physical environment attributes characteristics associated to geology, unconsolidated material and landforms, developed in accordance to adopted methodology at \"Escola de Engenharia de São Carlos\" (Zuquette, 1987). The tools \"Técnica de Avaliação de Terreno\" based at Lollo (1996), and the Geographical Information System (GIS-Idris 32) were to used optimization and confidence on the obtained results analysis handling of the information to generation cartographic documents. The cartographic documents were elaborated study area : Documentation Map; Geological Map; Declivities Chart; Unconsolidated Materials Map; Landforms Map; Drainage Network Map and General Geotecnical Zoning Map.

O estudo de impacto ambiental (EIA), diante da concepção de avaliação de impacto ambiental (AIA), determina, em seus objetivos, a necessidade de se demonstrar a viabilidade ambiental não só de projetos, mas também de políticas, planos e programas (PPP). Considerado atualmente como instrumento ambiental essencial a qualquer processo decisório, conceitualmente distingue-se por necessidades e respostas diferentes para PPP, daquelas previstas para projetos. No Brasil, a prática associada somente a projetos e desvinculada das decisões que ponderem as alternativas locacionais, tem demonstrado distorções de uso do instrumento EIA no que se refere a respostas e também à sua credibilidade. Esta prática se refletirá no estabelecimento de responsabilidades distintas quanto à geração e disponibilidade das informações, no entendimento do conceito de EIA, como também no universo de exigências a serem requeridas. No que se refere à articulação com outros instrumentos da PNMA, cabe ao zoneamento ecológico econômico (ZEE) um grande papel, qual seja, o de articulador ambiental das diferentes escalas da AIA e gerador do diagnóstico ambiental com cenários e possibilidades de prognóstico. Conceitualmente o ZEE indica, ambientalmente e de maneira prévia, todas as alternativas de localização, ao contemplar os fatores ambientais diante da capacidade de suporte do meio em relação a uma determinada atividade, além de ser mais adequado para delimitar a área de influência e/ou os conflitos. Portanto, o estabelecimento de universos mais claros para cada escala de abordagem do instrumento AIA e a possibilidade de articulação com o ZEE desobrigarão o EIA de respostas e compromissos de implicações relacionadas a políticas públicas ao subsidiar os empreendimentos públicos e privados. O presente trabalho avalia o instrumento AIA e a possibilidade de aproveitar a implementação do ZEE para melhorar o alcance e eficiência do EIA, e se configurar como mais um instrumento de contribuição à sustentabilidade ambiental / The environment impact statement (EIS), facing the concept environment impact assessment (EIA), settles, in its objectives, the need to demonstrate not only the environment viability of projects, but also of policies, plans and programs (PPP). Currently considered as essential environment instrument to any decision making process, conceptually EIA marks presence for necessities and different answers for PPP. In Brazil, the practice associated only to projects and out of the decisions that ponder the localization alternatives, has demonstrated distortions in the use of the EIS instrument in relation of its answers and also to its credibility. This practice will be reflected on the establishment of distinct responsibilities considering the generation and availability of information, in the agreement of the EIS concept, and also in the universe of requirements to be met. In relation to the joint action with other instruments of the PNMA, it gives to the economic ecological zoning (ZEE) an important role, which is, being the environmental articulator of different scales of the EIA and generator of environmental diagnosis with scenes and possibilities of prognostic. Conceptually the ZEE indicates, environmentally and previously way, all environmental factors facing localization alternatives, when contemplating the carrying capacity in relation to a determined activity, besides being more adjusted to delimit the area of influence and/or the conflicts. Therefore, the establishment of clearer universes for each scale of approaching the instrument EIA and the possibility of joint action with the ZEE will liberate the EIS from giving answers and commitments of related implications to public policies and subsidizing the enterprises. The present work evaluates the EIA instrument and the possibility and advantage of the implementation of the ZEE to enlarge the range and to improve the EIS efficiency, and to configure it as an additional contribution instrument to environmental sustainability