Nanoscale Structure and Interfacial Electrochemical Reactivity of Moiré-Engineered Atomic Layers

ConspectusThe electronic properties of atomically thin van der Waals (vdW) materials can be precisely manipulated by vertically stacking them with a controlled offset (for example, a rotational offset─i.e., twist─between the layers, or a small difference in lattice constant) to generate moiré superlattices. In recent years, the application of this "twistronics" concept to interfacial electrochemistry has unveiled unique pathways for tailoring the electrochemical reactivity. This Account provides an overview of our work that leveraged a suite of structural characterization methods, such as interferometric four-dimensional scanning transmission electron microscopy, dark-field transmission electron microscopy, and scanning tunneling microscopy, along with nanoscale electrochemical measurement techniques, namely, scanning electrochemical cell microscopy (SECCM), to uncover and dissect the profound impact of electrode electronic structure, controlled by interlayer twist, on interfacial electron transfer kinetics. At the heart of our findings is the discovery that moiré engineering enables the isolation of thermodynamically unfavorable stacking configurations, or topological defects, that substantially increase the standard electron transfer rate constant at the solid-liquid interface beyond what has been measured on conventional, nontwisted two-dimensional (2D) materials. This enhancement in interfacial reactivity can be attributed to the localization of a high density of electronic states within these particular sites in the superlattice, a similar effect to that which occurs upon incorporation of physical defects or vacancies in an electrode material but instead using an atomically pristine surface with a highly tunable structure. Throughout our studies, understanding the nuances of the relationship between the preimposed moiré twist angle and the observed electron transfer kinetics has heavily relied on the interrogation of additional factors such as spontaneous superlattice reconstruction and three-dimensional localization of electronic states, illustrating the importance of combining electrochemical measurements with both nanoscale structural probes and theoretical modeling for designing and optimizing moiré-engineered electrodes. The insight afforded by our efforts in this space continues to deepen our understanding of the fundamental mechanisms governing electron transfer at electrochemical interfaces at large and also points to the revolutionary prospect of twistronics for advancing electrochemical technologies. While our electrochemical studies have, so far, focused largely on graphene-based moiré materials, we also offer a perspective on the promise of transition metal dichalcogenide (TMD)-based moirés as candidates for highly versatile (photo)electrode surfaces. Accordingly, we provide a discussion of our studies on the structural relaxation observed in moiré superlattices of TMDs, and we summarize our work combining SECCM with field-effect electrostatic gating of TMDs to deconvolute the influences of material conductivity and intrinsic electron transfer kinetics from the overall electrochemical response of a semiconducting 2D material. Overall, this body of work establishes a distinctive foundation for the design of a wide range of materials with tailored properties that can provide crucial insights into interfacial charge transfer chemistry─potentially serving as platforms for sensing, energy conversion, and electrocatalysis─in addition to the emergent exotic correlated electron physics that originally ignited intense interest in moiré twistronics.