Effect of Supporting Pd Nanoparticles on WO_x Nanorods on Their Stability and Catalytic Activity Towards the Electrochemical Oxidation of Concentrated Formic Acid

Direct formic acid fuel cells (DFAFC) are considered one of the most promising fuel cells to penetrate the market due to their desired and unique properties. Formic acid (FA) could be easily produced from different sources (especially biomass) and is non-toxic. The FA-based fuel cell has a high open circuit potential in comparison to methanol and Ethanol 1 , high energy conversion efficiency, and fast kinetics. However, the major drawback that affects using DFAFCs is the catalysts' stability and reaction intermediates' poisoning effect, especially at high concentrations of FA. FA has a dual pathway mechanism: either the simple and desired pathway of direct oxidation to CO 2 2 or the unfavorable indirect oxidation to poisonous CO-like species that strongly adsorb on the catalyst surface, deactivating it, 3 before it is hardly oxidized in a second step to give CO 2 . Therefore, the catalyst should be designed to direct the reaction towards the direct pathway and facilitate the poisoning species removal. The most active catalyst for FA oxidation in acidic media is palladium 4 but it is highly susceptible to CO poisoning, especially as the FA concentration increases due to the high contribution of the indirect pathway. In addition, palladium nanoparticles supported on carbon material are known to suffer from dissolution in the acidic media making the electrode unstable for long-term application. 5 In this presentation, the synthesis of nonstoichiometric WOx nanorods using hydrothermal methods will be reported. The Pd nanoparticles are synthesized and loaded on the WOx nanorods using ethanol as both a solvent and a reducing agent to produce a surfactant-free Pd surface. The synthesized materials are evaluated using XRD, TEM, FT-IR, EDS, and XPS. The effect of WO x nanorods as catalyst support on Pd nanoparticles activity and stability towards the oxidation of different concentrations (1-4 M) of FA in acidic media are evaluated using cyclic voltammetry (CV) and chronopotentiometry (CP), and compared with that of carbon-supported Pd catalyst. The Pd behavior in both cases will be correlated to its chemical and physical properties and thoroughly discussed. References: J. Sun et al., RSC Adv. , 8 , 18619–18625 (2018). K. Jiang, H.-X. Zhang, S. Zou, and W.-B. Cai, Phys Chem Chem Phys , 16 , 20360–20376 (2014). T. Gunji and F. Matsumoto, Inorganics , 7 , 36 (2019). A. Gharib and A. Arab, Int. J. Hydrog. Energy , 46 , 3865–3875 (2021). T. Al Najjar, N. Ahmed, and E. N. El Sawy, RSC Adv. , 11 , 22842–22848 (2021).