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CaO promoted Graphene-Supported Palladium Nanocrystals as a Universal Electrocatalyst for Direct Liquid Fuel Cells.

In this article, we present the fabrication of reduced graphene oxide supported PdCa (PdCa/rGO) alloyed catalyst via NaBH4 reduction method as anode electrocatalyst for direct formic acid fuel cell in acidic medium and direct alcohol fuel cell in basic medium. Powder X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller (BET) surface analysis and Inductively coupled plasma mass spectrometry (ICP-MS) are used to characterize the PdCa/rGO catalyst. We demonstrate that the calcium oxide significantly enhances the electrocatalytic oxidation of methanol, ethanol and formic acid over Pd/rGO surface. The obtained mass activity for PdCa/rGO (4838.06 mA mg-1) is 1.97 times higher than Pd/rGO (2434.60 mA mg-1) for formic acid, PdCa/rGO (4674.70 mA mg-1) is 6.5 times higher than Pd/rGO (730.01 mA mg-1) for methanol, and PdCa/rGO (3906.49 mA mg-1) is 2.61 time higher than Pd/rGO (1490.08 mA mg-1) for ethanol, respectively. Low rate of CO poisoning, high activity, and long-term stability of PdCa/rGO electrocatalyst is attributed to the presence of calcium oxide. Cyclic voltammetry, chronoamperometry, square wave voltammetry and impedance results demonstrate that PdCa/rGO catalyst has superior catalytic activity for methanol, ethanol and formic acid oxidation as compared to Pd/rGO catalyst.