The fabrication of stable gold nanoparticle-modified interfaces for electrochemistry

Forming stable gold nanoparticle (AuNP)-modified surface is important for a number of applications including sensing and electrocatalysis. Herein, tethering AuNPs to glassy carbon (GC) surfaces using surface bound diazonium salts is investigated as a strategy to produce stable AuNP surfaces. GC electrodes are first modified with 4-aminophenyl (GC-Ph-NH₂), and then the terminal amine groups are converted to diazonium groups by incubating the GC-Ph-NH₂ interface in NaNO₂ and HCl solution to form a 4-phenyl diazonium chloride-modified interface (GC-Ph-N₂ ⁺Cl^-). Subsequently AuNPs are immobilized on the interface by electrochemical reduction to give a 4-phenyl AuNP-modified interface (GC-Ph-AuNP). For comparison, 4-aminophenyl AuNP- and 4-thiophenol AuNP-modified GC interfaces (GC-Ph-S-AuNP and GC-Ph-NH-AuNP), in which AuNPs are tethered to the surfaces by forming S-Au and NH-Au bond, respectively, were also prepared. Cyclic voltammetry, electrochemical impedance spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy are used to characterize these fabricated interfaces. The AuNP on GC-Ph-AuNP surfaces demonstrate good stability under sonication in Milli-Q water, during electrochemical treatment in 0.05 M H₂SO₄ solution, and over several weeks. By contrast, the GC-Ph-NH-AuNP and GC-Ph-S-AuNP surfaces showed significant particle losses under equivalent conditions.