Tuning Pd-to-Ag Ratio to Enhance the Synergistic Activity of Fly Ash-Supported PdAg Bimetallic Nanoparticles

Fly ash (FA)-supported bimetallic nanoparticles (PdAg/FA) with varying Pd:Ag ratios were prepared by coprecipitation of Pd and Ag involving in situ reduction of Pd(II) and Ag(I) salts in aqueous medium. All the supported nanoparticles were thoroughly characterized with the aid of powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), electron microscopy (field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM)), and elemental analyses, which include inductively coupled plasma-optical emission spectroscopy (ICP-OES) and energy-dispersive X-ray spectroscopy (EDS). A gradual broadening and shifting of PXRD peaks, ascribable to Ag, to higher angles with an increase in the Pd:Ag ratio affirms the alloying of interface between Pd and Ag nanoparticles. The coexistence of Pd and Ag was further confirmed by EDS elemental mapping as well as by the presence of bimetallic lattices on the FA surface, as evident from the high-resolution TEM analysis. The dependency of crystallite size and average size of bimetallic nanoparticles on Ag loading (mol %) was elucidated with the help of a combination of PXRD and TEM studies. Based on XPS analysis, the charge transfer phenomenon between contacting Pd-Ag sites could be evident from the shifting of 3d core electron binding energy for both Pd and Ag compared with monometallic Pd and Ag nanoparticles. Following a pseudo-first-order reaction kinetics, all the nanocatalysts were able to efficiently reduce 4-nitrophenol into 4-aminophenol in aqueous NaBH₄. The superior catalytic performance of the bimetallic nanocatalysts (PdAg/FA) over their monometallic (Pd₁₀₀/FA and Ag₁₀₀/FA) analogues has been demonstrated. Moreover, the tunable synergistic effect of the bimetallic systems has been explored in detail by varying the Pd:Ag mol ratio in a systematic manner which in turn allowed us to achieve an optimum reaction rate (k = 1.050 min^-1) for the nitrophenol reduction using a Pd₂₅Ag₇₅/FA system. Most importantly, all the bimetallic nanocatalysts explored here exhibited excellent normalized rate constants (K ≈ 6000-15,000 min^-1 mmol^-1) compared with other supported bimetallic Pd-Ag nanocatalysts reported in the literature.