Glassy carbon (GC) as a well-known electrode material has recently been proposed to consist of fullerene-like nanostructures. In order to verify the nanostructures in GC, find more physiochemical properties of GC, and develop sensors based on GC-related carbon nanomaterials, we investigated the morphologies and surface states of GC microspheres (GCMs) and their HNO3-oxidized products (ox-GCMs) with scanning electron microscopy (SEM), electrochemiluminescence (ECL), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and electron-paramagnetic resonance (EPR) spectroscopy. Our research results reveal that ox-GCMs rather than raw GCMs have abundant surface states, including many carboxyl groups (-COOH), surface defects (or carbon edges), and C-related dandling bonds. The surface states with a band gap of 2.14 eV endow ox-GCMs with strong cathodic ECL activity in the presence of peroxydisulfate (S2O82-). The ECL behaviors and maximum emission wavelength (580 nm) of ox-GCMs are very similar to those of small-sized graphene quantum dots and fullerene-like nanosheets, verifying that GCMs are essentially 3-D nanomaterials consisting of graphene or fullerene-like carbon nanostructures. It is for the first time that a microsized carbon material was reported to have good ECL activity in aqueous media. Possible mechanisms for surface state formation and ECL reactions are proposed for ox-GCMs, and a promising application of ox-GCMs in ECL immunosensing has been demonstrated by determining prostate specific antigen (PSA) as a model cancer biomarker.
Keywords: electrochemiluminesence; fullerene; glassy carbon; graphene quantum dots; immunoassay; prostate specific antigen; sensor.