Electrochemical Attachment of Diazonium-Generated Films on Nanoporous Gold

Nanoporous gold provides a high surface area platform for further chemistry, but the stability of the molecular linkages to the surface will limit applications. We attached aryl molecular layers to nanoporous gold electrodes through electrochemical reduction of the corresponding aryl-diazonium salt and studied the properties and stability of the resulting films in varied attachment conditions. Infrared reflection absorption spectroscopy and X-ray photoelectron spectroscopy were used to confirm the presence of the molecular layers. X-ray photoelectron spectroscopy indicates that the molecular layer is thick and that attachment conditions can form multilayers. However, cyclic voltammetry shows that the multilayers do not block electrochemical activity at the nanoporous gold surface. The molecular layers are resistant to replacement by alkane-thiol chains and exhibit some stability with respect to applied potential. These results indicate that a thick but highly defective molecular film forms with a mixture of strongly and weakly bound molecules.