Density Functional Theory Investigations of Metal/Oxide Interfaces and Transition Metal Catalysts

Paulami Majumdar, Purdue University

Abstract

One of the most important advances in modern theoretical surface science and catalysis research has been the advent of Ab-Initio Density Functional Theory (DFT). Based on the electronic structure formulation of Pierre Hohenberg, Walter Kohn and Lu Jeu Sham, DFT has revolutionized theoretical research in heterogeneous catalysis, electrocatalysis, batteries, as well as homogeneous catalysis using first-principles electronic structure simulations. Combined with statistical mechanics, kinetic theory, and experimental inputs, DFT provides a powerful technique for investigating surface structure, reaction mechanisms, understanding underlying reactivity trends, and using them for rational and predictive design of materials for various catalytic chemistries, including those that can propel us towards a clean energy future – for example water gas shift (WGS), methanol synthesis, oxidation reactions, CO2electroreduction, among many others. Fueled by advances in supercomputing facilities, numerous early and current DFT studies have been primarily focused on idealized simulations aimed at obtaining qualitative insights into experimental observations. However, as the immense potential of DFT has been unfolding, the demand for closer representation of realistic catalytic situations have rapidly emerged, and with it, the recognition of the need to reduce the disparity between theoretical DFT structures and real catalytic environments. Bridging this ‘materials gap’ necessitates using more rigorous catalyst structures in DFT calculations that can capture realistic experimental geometries, while at the same time, are creatively simplified to be computationally tractable. This thesis is a compilation of several projects on metals and metal/oxide systems that have been undertaken using DFT, in collaboration with experimental colleagues, with the goal of addressing some of the challenges in heterogeneous catalysis, while decreasing the ‘materials gap’ between theory and experiments. The first several chapters of this thesis focus on bifunctional, metal/oxide systems. These systems are quintessential in numerous heterogeneous catalysis applications and have been the subject of extensive study. More interestingly, they sometimes exhibit synergistic enhancement in rates that is greater than the sum of the individual rates on the metal (on an inert support) or on the oxide in isolation. Such bifunctionality often stems from the modified properties at the nanoscale interface between the metal and the oxide and is an active field of research. In particular, while a large body of literature exists that investigates the activity of metals, the role of the support in bifunctional systems is often uncertain and is the subject of investigation of the first few chapters of this thesis. We chose to study WGS on Au as support effects are particularly prominent on this system. The second chapter examines WGS on Au/ZnO, where realistic catalytic environment at the interface is reproduced by analyzing the thermodynamics of surface hydroxylation of the oxide under reaction conditions, and its effect on WGS kinetics is quantified through a microkinetic analysis. This study highlights the importance of considering spectator species which can drastically influence the energetics and kinetics of a reaction at a metal/oxide interface. In addition, fundamental aspects of the effect of surface hydroxyls on the electronic structure at the interface is also discussed.

Degree

Ph.D.

Advisors

Greeley, Purdue University.

Subject Area

Energy|Materials science

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