Dendritic multimetal architectures for efficient DME/MF electroconversion

Dimethyl ether (DME) and methyl formate (MF) are promising synthetic renewable fuels for energy systems aiming to enable circular energy conversion and storage. High hydrogen content, combined with a low boiling point, positions them as potential candidates for efficient on-site hydrogen generation and direct PEM fuel-cell applications. However, the lack of an efficient anode catalyst is the main bottleneck to the widespread adoption of these fuels. Herein, we developed an efficient metallic tin-supported bi-metallic and tri-metallic (Sn@Pt x Pd 1-x Sn 1.8) catalysts (X = 0-1), synthesized by electro-deposition and galvanic replacement reaction, for complete electro-conversion of DME and MF. By precisely tuning the platinum-to-palladium ratio, while keeping the total active metal content fixed, we were able to control the electro-catalytic reactivity and elucidate the specific role of each element in the anodic process. The multi-metal dendritic catalyst demonstrated a substantial negative shift in the onset potential, high -COad tolerance, unprecedented catalytic activity enhancement, and high stability under prolonged potential cycling. The high current activity (620 mAmg-1 PGM for MF and 165 mAmg-1 PGM for DME) was attributed to the cooperative effect of individual atoms on the catalyst surface. Herein, platinum provides adsorption and dehydrogenation sites, palladium promotes cleavage of the C-O-C backbone, and tin, along with the palladium atom, facilitates oxidative removal of poisoning.