Research Projects

This project aims to address the urgent global need for sustainable energy solutions by advancing next-generation CO₂ electroreduction technologies through a combined theoretical and experimental approach. It focuses on bridging recent theoretical advances in heterogeneous electron transfer (HET) kinetics with high-resolution in-situ electrochemical atomic force microscopy (EC-AFM) observations. While nanostructured metal electrodes, such as electrodeposited Cu, Ag, and Zn, have shown promise in enhancing CO₂ reduction reaction (CO₂RR) selectivity and efficiency, these improvements arise from complex multiphysics interactions that remain poorly understood. Factors such as electric double layer (EDL) reorganization, local surface curvature, step density, and atomic-scale defects significantly influence charge transfer, yet are not well-captured by traditional Marcus-based models. Leveraging recent models by Kant et al. that incorporate energy level alignment and frontier orbital theory, this project will develop analytical and multiscale models to quantify the role of atomic-scale surface features, curvature-modified work functions, and EDL coupling on HET kinetics. The theoretical component of the project is structured around four key objectives: (i) developing curvature- and structure-sensitive models for electron transfer on both pristine and modified electrodes; (ii) extending these models to electrodeposited and self-assembled surfaces; (iii) quantifying how chemisorption and site masking at kinks and steps influence CO₂ sticking probabilities and reduction kinetics; and (iv) formulating an impedance-based theory that captures the coupling of mesoscale EDL reorganization and atomic-scale morphology. Simultaneously, the experimental effort will fabricate well-defined metal nanostructures, such as nanopillars and step/kink-rich surfaces via controlled electrodeposition and galvanic replacement. In-situ EC-AFM will be used to monitor surface evolution under reaction conditions, enabling real-time correlation between morphological dynamics and kinetic metrics like exchange current densities and Tafel slopes. This combined approach enables direct mapping between theoretical predictions and observed electrocatalytic behavior. The project outcomes are expected to provide foundational insights into the role of nanoscale surface geometry and ionic environment on electron transfer kinetics in CO₂RR. Specifically, it will deliver: (1) a robust microscopic theory linking curvature, defects, and EDL structure to HET kinetics; (2) rational design guidelines for optimizing surface morphology, electrolyte composition, and solvent environment to enhance reaction selectivity and efficiency. Finally, the research will establish a theoretical-experimental feedback loop to accelerate the discovery and optimization of electrocatalysts for carbon conversion technologies.