In this presentation, we report on the utilization of first-principles based computational technique to study electrochemical CO₂ reduction mechanism on ligand protected metal nanoparticles. These materials are being pursued by the National Energy Technology Laboratory’s CO₂ Utilization Technologies program in the quest to develop more active and selective catalyst for CO₂ conversion into higher value products. We previously discovered an excellent CO₂ conversion catalyst based on negatively charged, ligand-protected Au₂₅(SC₂H₄Ph)₁₈^- nanoclusters. A significant finding from our modeling is that ligand-protected nanocatalysts must be activated through the creation of surface defects. The exposed metals site is then free to function as critical reaction center for the conversion of CO₂ into more valuable products. We have used this concept in our ongoing effort to understand the reduction process on ligand protected bimetallic Au-Cu nanoparticles. The reduction properties of such materials were experimentally found to be sensitive to the variation in the Cu content. Lastly, we present our ongoing investigation to predict trends in the activity of Ag, Au, Cu, Ir, Ni, Pd, Pt and Rh nanoparticles for CO₂ reduction. We specifically looked at different particle sizes to investigate its influence on the activity.