Covalent layer-by-layer functionalization of multiwalled carbon nanotubes by click chemistry

The covalent functionalization of multiwalled carbon nanotubes (MWNTs) by layer-by-layer (LbL) click chemistry is reported. The clickable polymers of poly(2-azidoethyl methacrylate) and poly(propargyl methacrylate) were synthesized at first by atom transfer radical polymerization (ATRP) of 2-azidoethyl methacrylate and reverse addition-fragmentation chain transfer (RAFT) polymerization of propargyl methacrylate, respectively. The two polymers were then alternately coated on alkyne-modified multiwalled carbon nanotubes using Cu(I)-catalyzed click reaction of Huisgen 1,3-dipolar cycloaddition between azides and alkynes. Thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) measurements confirm that the quantity and thickness of the clicked polymer shell on MWNTs can be well controlled by adjusting the cycles or numbers of click reaction and the polymer shell is uniform and even. X-ray photoelectron spectroscopy (XPS) and Fourier tranform infrared (FTIR) measurements showed that there were still a great amount of residual azido groups on the surfaces of the functionalized MWNTs after clicking three layers of polymers. Furthermore, alkyne-modified rhodamine B and monoalkyne-terminated polystyrene were subsequently used to functionalize the clickable polymer grafted MWNTs, giving rise to fluorescent carbon nanotubes (CNTs) and CNT-based polystyrene brushes, respectively. It demonstrates that the residual azido groups on the surfaces of MWNTs are available for further click reaction with various functional molecules.