(682g) Mechanistic Insights Towards Selective C3 Product Formation in CO(2)r on Copper

The electrochemical CO₂ reduction reaction on copper involves a plethora of competing reaction mechanisms, with the prospect of selectively forming three-carbon products like n-propanol. In this work, we use density functional theory (DFT) to determine the most competitive coupling mechanisms leading to C₃ products on Cu(100) and Cu(511). An exhaustive search across three different reduction pathways was performed. Our study suggests that there is more than one possible pathway towards forming C₃ intermediates. Our simulations show that much like C₂ formation, C₃ formation prefers stepped surfaces with (100)-like sites and that local field stabilization can play a pivotal role for certain coupling steps.