One-pot synthesis of Pd_20-xAu_x nanoparticles embedded in nitrogen doped graphene as high-performance electrocatalyst toward methanol oxidation

Mixed Pd–Au bimetallic nanoparticles embedded nitrogen doped graphene composites (PdAu/NG180) are explored for efficient electrocatalytic oxidation of methanol. A simple hydrothermal one-pot polyol method, involving simultaneous reduction of both Pd and Au, is utilized for the synthesis of Pd_20-xAu_x/NG180 (x wt % = 0, 5, 10 and 15). This method is of multiple advantages such as inexpensiveness, reagent-free and environment-friendly being surfactant free. The morphology, crystal structure and chemical composition of NG180, Pd/NG180 and Pd_20-xAu_x/NG180 catalysts are analyzed by XRD, FESEM-EDX, TEM, XPS and Raman spectroscopy methods. Electrocatalytic activities of PdAu/NG180 nanocomposites toward methanol oxidation reaction (MOR) in alkaline media are investigated by cyclic voltammetry, chronoamperometry and CO stripping measurements. Pd_20-xAu_x/NG180 exhibited an increase in the electroactive surface area of Pd to twice by the coexistence of Au. In cyclic voltammetry studies, Pd₁₀Au₁₀/NG180 catalyst exhibits highest peak current density for MOR and is 1.5 times highly efficient compared to Pd₂₀/NG180 with an enhanced shift in the onset potential by 140 mV to lower overpotentials. Besides, Pd₁₀Au₁₀/NG180 catalyst exhibited enhanced electroactive surface area and long-time durability in comparison to Pd₂₀/NG180 catalyst. The steady state current density for MOR observed with Pd₁₀Au₁₀/NG180 at the end of 4000 s (98 mA mg⁻¹_Pd) is higher than those observed with all the other catalysts at the end of mere 1000 s alone (97, 61, and 32 mA mg⁻¹_Pd). The promising high electrocatalytic activity of Pd₁₀Au₁₀/NG180 is well corroborated from CO stripping experiments that the specific adsorption of CO onto Pd₁₀Au₁₀/NG180 (0.71 C m⁻²) is merely half to that observed onto Pd₂₀/NG180 (1.49 C m⁻²).