Queen, Wendy LeeAsgari, Mehrdad2020-01-282020-01-282020-01-28202010.5075/epfl-thesis-7600https://infoscience.epfl.ch/handle/20.500.14299/164964Metal-Organic Frameworks (MOFs) are a class of porous materials that are applicable in many energy and environmentally relevant areas, due to their unique features including unprecedented internal surface areas and easy chemical tunability. Gas separation and storage are among the most important applications for which MOFs have been extensively studied. Considering the large number of potential MOFs that can be accessed, through a combination of numerous metal clusters and organic linkers, determining the relationship between their structural features (such as pore size and shape and chemical functionalities) and corresponding gas adsorption properties is of utmost importance. In this regard, in-situ characterization, especially diffraction, can be advantageous. MOFs can offer high crystallinity, and so their structure can readily be characterized via diffraction. In addition, due to the presence of metal ions, and predefined molecular building blocks, which exhibit multiple chemical moieties, the potential energy surface for a guest molecule within a MOF cavity possesses multiple minima that correspond to well-defined adsorption sites with varying binding energies. This makes diffraction the most direct way to probe static site-specific binding properties. Given this, the focus of this work is on understanding the structure-derived function of MOFs of interest in gas separation/storage applications. To do this, standard adsorption experiments are coupled with in-situ diffraction techniques. The latter is able to reveal the location and orientation of adsorbed guest species inside the framework, provide insights into the framework response to varying pressure, temperature, and atmosphere, and allow one to determine the relative differences in binding energy between neighboring adsorption sites. The aforementioned information can then be used to rationalize the relationship between different physiochemical features of a given framework and their performance in an adsorption process. In addition to establishing structure-property relations for the usage of MOFs, the obtained experimental results are used to corroborate those calculated by DFT methods, providing a stress test for computational methods aimed at predicting the structures and properties of hypothetical MOFs. The first chapter of this thesis, the introduction, offers a brief review of different characterization methods for studying gas adsorption/separation applications in MOFs. Although the focus of this chapter is on carbon dioxide capture as the application, these characterization methods are also used to study other adsorption processes. The next three chapters, chapters 2-4, present several prominent MOF families that are of interest in hydrogen storage and carbon dioxide capture applications. These case studies demonstrate how using in-situ diffraction techniques coupled with adsorption measurements and DFT calculations can be used to gain molecular level insight into how small molecules bind inside the selected MOF structures. Further, these structure-property correlation studies are able to help unveil how altering MOF building blocks, such as metals and ligands, gives rise to enhanced or diminished adsorption properties. The last chapter, chapter 5, is a study of the response of an activated MOF to varying temperature; in this chapter various structural motions, which are responsible for a large negative thermal expansion (NTE), are elucidated.enmetal-organic frameworksstructure-property relationship studyin-situ diffractiongas adsorptionchemical separationand gas storagethesis::doctoral thesis