Enhancement of the performance of Pd nanoclusters confined within ultrathin silica layers for formic acid oxidation

Abstract

The optimized design of highly active and stable anode electrocatalysts is essential for high performance direct formic acid fuel cells (DFAFCs). Herein, a facile and cost-effective strategy was proposed to fabricate a robust ultrasmall Pd nanocluster confined within ultrathin protective silica layers anchored on nitrogen doped reduced GO (NrGO) through generating amine functionalized graphene oxide with 3-aminopropyl triethoxysilane (APTES), followed by tuning the thickness of protective silica layers by precisely controlling the amount of tetraethylorthosilicate (TEOS). Amine functionalized graphene oxide generated by using APTES favors the formation of ultrasmall Pd nanoclusters due to the coordination of amine to PdCl₂⁴⁻ while the confinement effect of ultrathin protective silica layers stabilizes ultrasmall Pd nanoclusters and impedes the agglomeration and sintering of ultrasmall Pd nanoclusters during electrocatalysis. As a result, the ultrasmall Pd nanoclusters (∼1.4 nm) confined in silica layers on NrGO (Pd/NrGO@SiO₂) demonstrate a very high forward peak current density for formic acid oxidation (FAO) of 2.37 A mg⁻¹, outperforming the Pd/C catalyst (0.30 A mg⁻¹) and the Pd/rGO catalyst obtained by a conventional method (0.42 A mg⁻¹). More importantly, our confined Pd catalysts show the highest stability of only 5% inconspicuous degradation of the initial mass activity after 1000 cycles, compared with Pd/C (almost 100% loss), Pd/rGO (61.5% loss) and Pd/NrGO (73.2% loss). These strategies in this work provide a new prospect for the design of excellent noble catalysts to overcome the challenges in the practical application of DFAFCs.