The lack of electrocatalysts for the formate oxidation reaction (FOR) hampers the deployment of direct formate fuel cells (DFFCs). To overcome this limitation, herein, we detail the production of palladium hydride particles supported on C2N (PdH0.58@C2N) via a facile method. PdH0.58@C2N displays excellent FOR performance, reaching current densities up to 5.6 A·mgPd–1 and stable cycling and chronoamperometric operation. The Pd lattice expands due to the hydrogen intercalation. Besides, an electronic redistribution associated with the distinct electronegativity of Pd and H is observed. Both phenomena modify the electron energy levels, enhancing the activity and stability of the composite catalyst. More specifically, differential functional theory calculations show H intercalation to downshift the Pd d-band center in Pd0.58@C2N, weakening adsorbate binding and accelerating the FOR rate-determining step.

11 pages. -- Experimental Section. Chemicals. -- Synthesis of Hexaaminobenzene (HAB). -- Synthesis of C2N. --Synthesis of PdH0.58@C2N, Pd@C2N, PdH0.58 and PdH0.58/C2N. -- -- Structural characterization. -- Electrochemical Measurements. -- Computational method. -- Figures S1-S8. -- Table S1. Summary of the FOR activity and stability of Pd-based nanoalloys.

Peer reviewed