Hydrogen Generation from Additive-Free Formic Acid Decomposition Under Mild Conditions by Pd/C: Experimental and DFT Studies.

Safe and efficient hydrogen generation and storage has received much attention in recent years. Herein, a commercial 5 wt% Pd/C catalyst has been investigated for the catalytic, additive-free decomposition of formic acid at mild conditions, and the experimental parameters affecting the process systematically have been investigated and optimised. The 5 wt% Pd/C catalyst exhibited a remarkable 99.9% H selectivity and a high catalytic activity (TOF = 1136 h) at 30 °C toward the selective dehydrogenation of formic acid to H and CO. The present commercial catalyst demonstrates to be a promising candidate for the efficient in-situ hydrogen generation at mild conditions possibiliting practical applications of formic acid systems on fuel cells. Finally DFT studies have been carried out to provide insights into the reactivity and decomposition of formic acid along with the two-reaction pathways on the Pd (111) surface.