Boosting the Transesterification Reaction by Adding a Single Na Atom into g-C₃N₄ Catalyst for Biodiesel Production: A First-Principles Study

Increasing environmental problems and the energy crisis have led to interest in the development of alternative energy. One of the most promising sustainable alternatives to fossil fuel is biodiesel which is typically produced from the transesterification of refined vegetable oils using a homogeneous base catalyst. However, the current process limitations and steep production costs associated with the use of homogeneous catalysts have limited the global-wide acceptance of biodiesel. Heterogeneous catalysts have been considered suitable alternatives, but they still suffer from low catalytic activity. In this study, by using density functional theory (DFT) calculations, we examined the electronic and catalytic activity of the single Na-doped graphitic carbon nitrides (indicated by Na-doped g-C₃N₄) toward the efficient biodiesel (acetic acid methyl ester) production via the transesterification of triglyceride (triacetin). Our DFT calculation on reaction energetics and barriers revealed the enhancement of biodiesel productivity in the Na-doped catalyst compared to the pristine g-C₃N₄ catalyst. This was related to the large reduction of the barrier in the rate-limiting step. In addition, we investigated the acidity/basicity and electron distribution and density of state for the Na-doped and pristine g-C₃N₄ catalysts to better understand the role of the Na atom in determining the transesterification reaction. This study highlights the importance of the dopant in a g-C₃N₄ catalyst in determining the transesterification reaction, which may open new routes to improve biodiesel production.