Block Copolymer Templated Nitrogen-Enriched Nanocarbons: From Controlled Synthesis and Characterization, to Applications

The development of nanostructured carbon materials from PAN precursors is discussed in Chapter 1. Particular emphasis is placed on the rational structural design of PAN containing polymeric precursors developed in the Matyjaszewski and Kowalewski groups, while the detailed synthetic methodology will be discussed in the subsequent chapters.;Controlled synthesis is the prerequisite for many applications. The successful preparation of block copolymers via RDRP requires preparation of a macroinitiator with preserved chain end functionality (CEF). Work described in Chapter 2 resulted in the establishment of a universal rule for quantifying the CEF in all RDRPs, which is also the most important criterion for determining the "livingness" and degree of control over the polymerization. The parameters affecting the level of CEF preservation are determined.;Another challenge in ATRP is diminishing the concentration of catalyst employed during the polymerization procedure in order to reduce the cost and simplify the purification steps. Chapter 3 describes the systematic study of RDRP in the presence of zerovalent copper, which offers significant advantages in this regard. The contribution of all of the potential reactions occurring in an ATRP carried out in the presence of copper zero were evaluated, and a supplemental activator and reducing agent (SARA) ATRP mechanism is concluded to precisely describe this system. How to conduct and optimize SARA ATRP system is then demonstrated.;Chapter 4 is focused on another aspect of the robust capability of ATRP: controlling the molecular weight distribution. Activator regeneration electron transfer (ARGET) ATRP was employed to prepare polystyrene-block-poly(methyl acrylate) copolymers with tunable dispersity in the range of 1.32 to 2.0 for each block.;Knowledge attained from the studies discussed in Chapter 2 to 4 has been extensively utilized in the studies of nanocarbons. Chapter 5 discusses the preparation of a series of PAN containing diblock copolymers that were used as precursors for the preparation of nanocarbons. The block copolymers undergo phase separation and then the poly(n-butyl acrylate) serves as a sacrificial segment upon pyrolysis. Both thin film and bulk nanocarbons with diverse morphologies, resembling the original phase-separated copolymer precursors, were prepared. The carbonization of bulk copolymer precursors with branched PAN domains was of particular interest; which resulted in the formation of porous nanocarbons with large surface area and highly accessible nitrogen functionality originating from PAN.;Chapter 6 illustrates how porosity and accessible nitrogen functionality in the nanocarbon introduced in Chapter 5 can be utilized for CO2 capture. The main emphasis was placed on the surface area and nitrogen content's influence on adsorption capacity and selectivity was studied.;Chapter 7 discusses the application of PAN-derived nanocarbons as electrode materials for supercapacitors. Materials displaying both high energy density and high power density were achieved. This excellent performance was partially due to the mesoporous structure with high specific surface area, in combination with the pseudocapacitance originating from graphitic edge nitrogens.;Evidence of electrochemical activity of the nitrogen heteroatoms provided the motivation to explore the performance of copolymer templated nanocarbon as an electrocatalyst for oxygen reduction, as described in Chapter 8. A desirable 4-electron transfer process with a low overpotential system was achieved by as-prepared nanocarbon film with porous morphology; which again, demonstrates one of the unique properties of nanocarbons prepared from PAN containing block copolymer precursors.;*****Abstract Shortened*******.