Effects of Heteroatom Doping on the Electrochemical Hydrogen Uptake and Release of Pd-Decorated Reduced Graphene Oxide.

ABSTRACT

Heteroatom doping has been widely recognized as a key strategy for improving the electrochemical properties of graphene-based materials for hydrogen storage. However, a precise understanding of how heteroatom doping influences catalytic performance, specifically regarding the intricate effects of doping-induced electron redistribution, has been lacking. Here, we report on a comprehensive exploration of the electrochemical performance enhancement in Pd-decorated reduced graphene oxide (rGO) nanocomposites through fluorine (F) or nitrogen (N) doping. Various analytical techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray (EDX) spectroscopy, Raman spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) were employed to thoroughly characterize the synthesized nanocomposites. The findings revealed that either F or N doping effectively addressed clustering issues of Pd nanoparticles formed on the rGO surface, resulting in improved homogeneity of Pd distribution. Electrochemical studies provided crucial insights into hydrogen adsorption-desorption behaviors. The heteroatom doped nanocomposites, Pd/N-rGO and Pd/F-rGO, exhibited superior electrochemical performance, which can be attributed to the increase of the active sites due to the N-/F-doping, respectively. The hydrogen discharge capacities of Pd/N-rGO (80.9 mAh g-1) and Pd/F-rGO (25.0 mAh g-1) nanocomposites were determined to be over 4.0 and 1.2 times higher than that of the Pd/rGO (20.1 mAh g-1), respectively. The distinctive electrochemical performances observed between the two types of heteroatom-containing nanocomposites highlight the subtle structural modifications of Pd nanoparticles as the key factor influencing performance. This research contributes essential knowledge to the evolving field of hydrogen storage materials, emphasizing the promising potential of heteroatom-doped Pd-decorated rGO nanocomposites for advancing clean and sustainable energy solutions.