Abstract:
The rising demand for portable energy conversion devices has spurred the advancement of direct liquid fuel cells (DLFCs) employing fuels such as alcohol, ammonia, hydrazine, and vitamin C. Various precious metal platforms have been explored to increase the de-electronation kinetics and reduce catalyst poisoning but with substantial cost implications. We demonstrate the crucial role of ligands in non-precious organometallic complexes in influencing the de-electronation kinetics of fuel molecules through a unique substrate-ligand synergistic interaction. This unique chemistry imparts electron deficiency at the catalytic metal center while simultaneously populating the ligand with an extensive proton charge assembly. This distinct substrate-ligand interaction enhances the DLFC performance by coulombically dragging the substrate with a distinct amplification in its de-electronation kinetics. By integrating this approach with an outer-sphere half-cell reaction, a precious metal-free vitamin C fuel cell is developed, which is capable of generating an open circuit voltage of ∼950 mV, a peak power density of ∼97 mW/cm2 at a peak current density of ∼215 mA/cm2 with the performance metrics nearly 1.7 times higher than a precious metal based DLFC. This highlights the potential of substrate-ligand synergy in the design of efficient molecular catalysts for energy conversion applications.