Document Type

Dissertation

Date of Award

8-31-2021

Degree Name

Doctor of Philosophy in Chemical Engineering - (Ph.D.)

Department

Chemical and Materials Engineering

First Advisor

Gennady Gor

Second Advisor

Edward L. Dreyzin

Third Advisor

Alexei Khalizov

Fourth Advisor

Joshua Young

Fifth Advisor

Christopher Rasmusse

Abstract

The dissertation studies methods for mesoporous materials characterization using adsorption at various levels of scale and complexity. It starts with the topic introduction, necessary notations and definitions, recognized standards, and a literature review.

Synthesis of novel materials requires tailoring of the characterization methods and their thorough testing. The second chapter presents a nitrogen adsorption characterization study for silica colloidal crystals (synthetic opals). These materials have cage-like pores in the range of tens of nanometers. The adsorption model can be described within a macroscopic approach, based on the Derjaguin-Broekhoff-de Boer (DBdB) theory of capillary condensation. A kernel of theoretical isotherms is built and applied to the solution of the adsorption integral equation to derive the pore-size distribution from experimental data. The technique is validated with a surface modification of the samples so that it changes the interaction but not the pore size.

The second chapter deals with the characterization of three-dimensional ordered mesoporous (3DOm) carbons. Similar to opals, these materials have cage-like mesopores, however, these pores are connected with large windows. These windows affect the adsorption process and calculated pore-size distributions. The grand canonical Monte Carlo simulations with derived solid-fluid potentials, which take into account the 3DOm carbons geometry, confirm the critical role of interconnections, their size, and number, for correct interpretation of adsorption data for the PSD calculations.

The fourth chapter discusses a method for the pore size estimation that can serve as an alternative to the adsorption isotherms analysis. It is based on measurements of elastic properties of liquid that can be useful for the pore size estimation. A Vycor glass sample, a disordered mesoporous material with channel-like pores having a characteristic size of ca. 6-8 nm, is considered. The changes in longitudinal and shear moduli from the experimental data and molecular simulations are predicted with a near-quantitative agreement. Then, it follows by their relation of the moduli to the pore size, which is promising for characterization.

The last fifth chapter considers a promising Monte Carlo method, the Kinetic Monte Carlo (kMC) algorithm. This method is efficient for the vapor-liquid equilibrium prediction in dense regions. This chapter shows a benchmark with conventional Metropolis et al algorithms as well as a parallelization scheme of the kMC algorithm.

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