Unusual Reactivity of Graphene Quantum Dot-Wrapped Silver Nanoparticles with Hg(II): Spontaneous Growth of Hg Flowers and Their Electrocatalytic Activity.

The galvanic reaction (GR) between a graphene quantum dot (GQD)-stabilized AgNP (Ag-GQD)-modified glassy carbon (GC) surface and Hg(II) leads to complete dissolution of AgNPs within 15 min and subsequent growth of Hg(0) as a "flower" on the GQD surface. This is unusual because generally the GR of bulk Ag/AgNPs with Hg(II) leads to the formation of a Hg-Ag amalgam/core shell structure. The appearance of peaks at 99.9 and 103.9 eV in X-ray photoelectron spectroscopy confirms Hg(0) on GQDs, whereas the disappearance of a peak at 370 eV indicates complete dissolution of Ag(0). When 200 ppm Hg(II) interacts with Ag-GQDs for 10 min, coalescence of AgNPs takes place along with the formation of Hg(0) petals separately. However, Hg(0) is grown as a flower with 2 μm size, and complete dissolution of AgNPs occurs subsequently after 15 min. The reason for anti-amalgamation is the direct deposition of Hg(0) by the available oxygen functional groups, followed by its strong adsorption on the graphene surface of GQDs. The subsequent growth of Hg(0) as a flower is due to the GR between AgNPs and Hg(II). Interestingly, the Hg flower-GQD-modified GC electrode acts as a good electrocatalyst toward HO reduction by decreasing its overpotential by 150 mV in contrast to GC/Ag-GQDs.