Electrochemiluminescence revealing that HNO3-oxidized single-walled carbon nanotubes are essentially tubular graphene quantum dot-nanoassemblies

Abstract

Graphene quantum dots (GQDs) as recently emerging 0-D graphitic nanomaterials, have attracted much attention due to their unique optical, electrical and catalytic properties. However, some properties of GQDs, such as very small size, low density, and excellent water-solubility, make it difficult to be separated and immobilized. This may limit the recycle and purification of GQDs, and thus their applications in catalysis and sensing. In this work, we prepared tubular GQD-nanoassemblies (t-GQD-NAs) by etching single-walled carbon nanotubes (SWCNTs) with concentrated HNO3. The synthesized t-GQD-NAs were characterized by TEM, SEM, XPS, Raman spectroscopy and electrochemiluminescence (ECL) in details. t-GQD-NAs were much shorter and slimmer in morphology, bore more oxygen-containing groups, and had a higher surface defect density compared with SWCNTs. t-GQD-NAs not only maintained good UV absorption property of SWCNTs but also showed strong infrared ECL emission and broad ECL spectrum, verifying that t-GQD-NAs were assembled from GQDs of various sizes and some graphene nanoribbons. This is for the first time that 0-D GQDs were reported to be assembled into 1-D tubular carbon structures. The t-GQD-NAs with abundant surface states and good ECL activity could be easily separated, purified, and immobilized, suggesting their promising applications in ECL sensing and catalysis.