DFT and Microkinetic Comparison of Ru-Doped Porphyrin-like Graphene and Nanotubes toward Catalytic Formic Acid Decomposition and Formation

Immobilization of single metal atoms on a solid host opens numerous possibilities for catalyst designs. If that host is a two-dimensional sheet, sheet curvature becomes a design parameter potentially complementary to host and metal composition. Here, we use a combination of density functional theory calculations and microkinetic modeling to compare the mechanisms and kinetics of formic acid decomposition and formation, chosen for their relevance as a potential hydrogen storage medium, over single Ru atoms anchored to pyridinic nitrogen in a planar graphene flake (RuN4-G) and curved carbon nanotube (RuN4-CNT). Activation barriers are lowered and the predicted turnover frequencies are increased over RuN4-CNT relative to RuN4-CNT. The results highlight the potential of curvature control as a means to achieve high performance and robust catalysts.

Automated summary

This study investigates the mechanisms and kinetics of formic acid decomposition and formation over single Ru atoms anchored on pyridinic nitrogen in a planar graphene flake and curved carbon nanotubes. The results show that curvature control has the potential to enhance catalytic performance.