Document Type



Doctor of Philosophy


Chemical Engineering

First Adviser

Snyder, Mark

Other advisers/committee members

Snyder, Mark; Caram, Hugo; Gilchrist, James; Landskron, Kai


Hierarchical control over pore size, pore topology, and meso/mictrostructure as well as material morphology (e.g., powders, monoliths, thin films) is crucial for meeting diverse materials needs among applications spanning next generation catalysts, sensors, batteries, sorbents, etc. The overarching goal of this thesis is to establish fundamental mechanistic insight enabling new strategies for realizing such hierarchical textural control for carbon materials that is not currently achievable with sacrificial pore formation by `one-pot' surfactant-based `soft'-templating or multi-step inorganic `hard-templating. While `hard'-templating is often tacitly discounted based upon its perceived complexity, it offers potential for overcoming key `soft'-templating challenges, including bolstering pore stability, accommodating a more versatile palette of replica precursors, realizing ordered/spanning porosity in the case of porous thin films, simplifying formation of bi-continuous pore topologies, and inducing microstructure control within porous replica materials. In this thesis, we establish strategies for hard-templating of hierarchically porous and structured carbon powders and tunable thin films by both multi-step hard-templating and a new `one-pot' template-replica precursor co-assembly process. We first develop a nominal hard-templating technique to successfully prepare three-dimensionally ordered mesoporous (3DOm) and 3DOm-supported microporous carbon thin films by exploiting our ability to synthesize and assemble size-tunable silica nanoparticles into scalable, colloidal crystalline thin film templates of tunable mono- to multi-layer thickness. This robust thin film template accommodates liquid and/or vapor-phase infiltration, polymerization, and pyrolysis of various carbon sources without pore contraction and/or collapse upon template sacrifice. The result is robust, flexible 3DOm or 3DOm-supported ultra-thin microporous films that can be transferred by stamp techniques to various substrates for low-cost counter-electrodes in dye-sensitized solar cells, as we demonstrate, or as potential high-flux membranes for molecular separations. Inspired by `one-pot' `soft'-templating approaches, wherein the pore forming agent and replica precursor are co-assembled, we establish how `hard'-templating can be carried out in an analogous fashion. Namely, we show how pre-formed silica nanoparticles can be co-assembled from aqueous solutions with a carbon source (glucose), leading to elucidation of a pseudo-phase behavior in which we identify an operating window for synthesis of hierarchically bi-continuous carbon films. Systematic study of the association of carbon precursors with the silica particles in combination with transient coating experiments reveals mechanistic insight into how silica-adsorbed carbon precursor modulates particle assembly and ultimately controls template particle d-spacing. We uncover a critical d-spacing defining the boundary between ordered and disordered mesoporosity within the resulting films. We ultimately extend this thin-film mechanistic insight to realize `one'-pot, bi-continuous 3DOm carbon powders. Through a combination of X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and high-resolution transmission electron microscopy (HR-TEM), we elucidate novel synthesis-structure relations for template-mediated microstructuring of the 3DOm replica carbons. Attractive properties of the resulting bi-continuous porous carbons for applications, for example, as novel electrodes, include high surface areas, large mesopore volumes, and tunable graphitic content (i.e. >50%) and character. We specifically demonstrate their performance, in thin film form, as counter-electrodes in dye-sensitized solar cells. We also demonstrate how they can be exploited in powder form as high-performance supercapacitor electrodes exhibiting attractive retention and absolute capacitance. We conclude the thesis by demonstrating the versatility of both the thin-film and powder templating processes developed herein, for realizing ordered binary colloidal crystal templates and their bi-modal porous carbon replica films, expanding compositional diversity of the `one-pot' thin film process beyond carbons to include an example of 3DOm ZrO2 films, and employing the hard-templating process as a strategy for realizing 3DOm carbon-supported nanocarbides.