Direct formic acid fuel cells (DFAFCs) are one of the most promising power sources due to its high conversion efficiency; relatively low carbon emissions, toxicity, and flammability; convenience; and low-cost storage and transportation. However, the key challenge to large-scale commercial applications is its poor power performance and the catalyst’s high preparation cost. In this study, a new sandwich-structured Pd/polypyrrole-graphene/Pd (Pd/PPy-Gns/Pd)-modified glassy carbon electrode (GCE) was prepared using a simple constant potential (CP) electrodeposition technique. On the basis of the unique synthetic procedure and structural advantages, the Pd/PPy-Gns/Pd shows a fast charge/mass transport rate, high electrocatalytic activity, and great stability for formic acid electro-oxidation (FAO). The mass activity of Pd/PPy-Gns/Pd electrode reaches 917 mA·mg−1Pd. The excellent catalytic activity is mainly due to the uniform embedding of Pd nanoparticles on the polypyrrole-graphene (PPy-Gns) support, which exposes more active sites, and prevents the shedding and inactivation of Pd nanoparticles. At the same time, the introduction of graphene (Gns) in the PPy further improved the conductivity of the catalyst and accelerated the transfer of electrons.

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