Zhichao, Liu2026-06-022026-06-022026-06-022026-05-29https://hdl.handle.net/10012/23516This dissertation addresses two challenges in heterogeneous redox reactions of metal oxide materials, namely the reaction mechanism of Al-based energetic nanothermites and the in-situ production of water using lunar oxide materials. Although extensive theoretical and experimental efforts have been focused on both topics, a complete mechanistic understanding of the reaction mechanisms in both topics remains lacking. The first part of this work focuses on the fundamental reaction mechanisms of Al-based nanothermites, with emphasis on the typical system of Al/CuO. Despite extensive experimental and theoretical studies, the exact ion transport pathways and rate-limiting steps remain unclear because nanothermite reactions involve coupled redox processes, phase transformations, heat release, and ion transport across dynamically evolving condensedphase interfaces. In particular, the naturally formed amorphous alumina layer on Al, as the rate-limiting phase, is expected to play a crucial role in governing oxygen transport, interfacial redox chemistry, and ignition behavior. However, the mechanistic contribution of the surface amorphous alumina layer is still not fully understood. This dissertation establishes a mechanistic framework for heterogeneous redox reactions in Al-based nanothermites through systematic investigations of oxygen migration across representative bulk phases and key interfaces. The results identify the rate-controlling and exothermic steps that govern oxygen transport and ignition, and connect the proposed atomistic mechanisms to experimentally observed preignition behavior, reaction kinetics, and the wide range of reported activation barriers. The second part of this work addresses the data-driven discovery of lunar oxide materials for Solar-Wind (SW)-derived H retention and subsequent water production, especially in sunlit lunar regions. Although increasing evidence suggests that hydrogen implanted by SW can be retained in lunar mineral rims and converted to molecular water, the underlying mechanisms that govern H retention and H₂O formation remain poorly understood. In addition, the large elemental space of lunar-based oxides makes the experimental identification of promising materials highly challenging. To address this issue, this dissertation develops a data-driven materials discovery framework that integrates Density Functional Theory (DFT) calculations, materials databases, and Machine Learning (ML) models to evaluate local reaction energetics and materials screening criteria, which include H insertion energy, H₂O formation energy, H diffusion length, and the fugacity ratio of H₂O to H₂ to identify promising candidate materials. By applying these criteria, eleven high-/mixed-valence Fe-bearing oxides, together with lunar magnetite, are identified as promising materials for SW-implanted H retention and in-situ H₂O production, while most of the Fe²⁺-bearing lunar minerals are found to be intrinsically unfavorable for in-situ H₂O production. Overall, this dissertation provides new mechanistic insights into heterogeneous redox reactions in energetic and planetary oxide materials systems. The findings advance the fundamental understanding of nanothermite ignition and combustion, while also establishing a predictive framework for discovering lunar materials capable of supporting the future In-Situ Resource Utilization (ISRU).enNATURAL SCIENCES::Chemistry::Theoretical chemistry::Quantum chemistryTECHNOLOGY::Materials scienceDoctoral Thesis