Thesis advisor: Jeffery A. Byers / Thesis advisor: Petter Zhang / This thesis discusses the development of a surface-initiated N-carboxyanhydride (NCA) polymerization system from a redox-switchable catalyst for polyamide synthesis and further efforts towards the synthesis of polypeptide-based materials through the integration of NCA synthesis and its polymerization. In Chapter one, the most used methods to obtain polypeptide-based materials as well as their significant limitations are introduced. A new strategy is presented to access the polypeptide-based materials based on the integrated catalysis under spatial and temporal control. In Chapter two, a strategy to allow the attachment of a redox-switchable NCA polymerization catalyst on surface of titania for the synthesis of polyamide brushes will be demonstrated. Investigations about the kinetics of this surface-initiated ring-opening polymerization will be presented by carrying out the reaction in batch and under flow. Chapter three will discuss efforts towards achieving the integration of NCA synthesis and NCA polymerization, which includes an additional anchoring method to support polymerization catalyst and compatibility tests between the two separate reactions. / Thesis (MS) — Boston College, 2022. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Thesis advisor: Dunwei Wang / Thesis advisor: Matthias Waegele / Lithium metal anode (LMA) holds great promise as alternative anode material for next-generation high energy density batteries. Efficiency and safety are two most critical concerns that impede practical application of LMA due to unstable interface between the electrode and the electrolyte. Solid electrolyte interphase (SEI), a passivation layer formed from electrolyte decompositions on the LMA surface, dictates the chemical and mechanical evolution of the electrode/electrolyte interface, and therefore directly affect the cycle life of lithium metal batteries. Although significant progress has been achieved to improve battery performance, a thorough understanding of SEI functions and properties is still inadequate. Both compositional and structural complexity severely hinder the efforts to uncover the SEI formation and evolution mechanism. To achieve stable lithium plating and stripping over cycling, it is necessary to lay a foundation of composition-structure-property relationships that can guide rational design of ideal SEI.First, to solve the safety and efficiency issues simultaneously, a facile and effective way to enable LMA in nonflammable electrolyte was identified by simply introducing oxygen into the battery. Reversible lithium plating and stripping was realized in a flame retardant triethyl phosphate solvent otherwise incompatible to LMA. A unique electrochemically induced electrolyte decomposition pathway was proposed and studied computationally and experimentally. The SEI formation mechanism enriches the knowledge of on the complex reactions toward an ideal SEI. The operation of Li-O2 batteries and Li-ion batteries were also demonstrated in a nonflammable phosphate electrolyte system. To understand the unique role of different SEI compositions, in the second part of this thesis, we designed and synthesized two-component artificial SEI model structures for comparison study. Our central hypothesis is that tailoring LiF and Li3PO4 compositions in the SEI layer can achieve a balanced and improved electrode/electrolyte stability. A magnetron sputtering method was developed to prepare LiF and Li3PO4 mixture films on Cu substrate. Preliminary results from battery cycling tests shows that mixture SEI structure is correlated to improved Coulumbic efficiency. Next, to understand detailed Li+ ion transport properties of the SEI. We presented an outline the current understanding of Li+ ion transport mechanisms and their dependence on the SEI. We also built on this fundamental knowledge to discuss practical effects in experimental systems. Lastly, we shared our perspectives on critical remaining questions in this field. In parallel to study on electrochemical energy system, developing electrochemical methods for integrated catalysis constitutes another part of thesis. We demonstrated that reactivity of an immobilized iron catalyst could be altered by application of an electrochemical potential to a surface to enable polymerization of different classes of monomers. A method was developed to pattern functional surfaces by using electrochemical potential to activate and deactivate polymerization reactions. The orthogonal reactivity of switchable polymerization catalysts was utilized to create patterned surfaces functionalized with two different polymers initiated from mixtures of monomers. / Thesis (PhD) — Boston College, 2022. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.