UC Berkeley

Understanding the fundamental factors that govern heterogeneous electron transfer (ET) at solid–electrolyte interfaces is critical for the rational design of electrochemical systems for energy conversion and catalysis. This dissertation establishes a mechanistic framework for understanding and controlling ET at electrochemical interfaces by quantitatively linking electrode electronic structure to interfacial reactivity. Central to this work is the development and validation of a unifying hypothesis: the electrode density of states (DOS) serves as a primary determinant of both reaction kinetics and catalytic selectivity. By leveraging the unique tunability of low-dimensional van der Waals materials, such as transition metal dichalcogenides and graphene-based heterostructures and moiré superlattices, this research demonstrates that electrostatic gating (implemented via field effect or crystalline dopants) can be employed as a purely electronic means to modulate catalytic activity without altering the chemical identity of the surface. A key theoretical advancement presented herein is the identification of a previously ignored electronic contribution to the reorganization energy, where the screening properties and DOS of the electrode actively shape the energetic landscape of electron exchange. Furthermore, the integration of these insights into gated device architectures enables the precise alignment of sharp DOS enhancements with molecular redox potentials, providing a foundation for the design of switchable catalytic interfaces with programmable function. Ultimately, this work bridges the gap between microscopic electronic properties and macroscopic electrochemical behavior, offering a new paradigm for the rational design of next-generation energy conversion and catalytic systems.