Publication
Sorbent are the workhorses of most contemporary separation processes. Crystalline sorbents boast descript structures that facilitate in silico study. Their diversity is matched by their varied applications. At the forefront of their currently researched applications is direct air capture (DAC). The looming consequences climate change propel the urgent research of DAC extraction processes. They pose a unique challenge given the unprecedented scale of the task. The rapidly growing number of crystalline sorbents and their large number of applications overwhelm the field. Serendipitous discoveries are as inefficient as slow, for all applications. The urgency of DAC research makes this especially troubling. Furthermore, the scale of DAC processes demands holistic assessment of DAC sorbents. It makes their environmental impact, their cost, and the energy demand of their processes non-negligible. Their scale may also slow the rollout and replacement of these technologies. Systematic, expedited, solutions are, therefore, a must. In this work, modular approaches are explored for the conscious advancement of crystalline sorbent research. Modules are units that map to physical or chemical features. Modules may not be delimited arbitrarily. Their independence needs to hold in the context of the research question. This allows for the reduction of elaborate problems to the collection of contributions from modules. This independence is signified by orthogonality. This is a prerequisite to dissect and combinatorially recompose structures, and to study modules in isolation. Modular approaches are here showcased for material physical properties, separation of structure and function, synthesis, retrosynthesis, and material design. Specific heat of crystalline sorbents is a key parameter for screening sorbents for processes with a temperature-swing component. Experimental validation is provided for the in silico prediction of the specific heat of metal-organic frameworks (MOFs). The latter relied on the treatment atoms in their chemical environments as modules. Orthogonality of the structural frame and the functional decorations is studied for the post-synthetic modification of MOFs. Both chemical and steric orthogonality are addressed. Chemical orthogonality is further observed for modifier moieties, resulting in a statistical set of modification products. An ample characterization toolbox for nonuniform MOF modifications is provided. A pressing roadblock for the computational-experimental material discovery loop is MOF retrosynthesis. This is addressed by the didactic curation of solvothermal MOF syntheses. Features pertinent to supramolecular interactions are selected, backed by validation. The organic continuum of covalent organic frameworks (COFs) makes delimiting their structural modules non-trivial. An in-depth retrosynthetic review and subsequent systematic analysis is provided to unlock modular studies in their material space.