Nanoporous gold electrodes modified with self-assembled monolayers for electrochemical control of the surface charge

Abstract

The electrochemical behaviour of nanoporous gold modified with self-assembled monolayers is investigated with regard to its point of zero charge (pzc) and proton transfer reaction. Due to their high surface-to-volume ratio and conductivity, nanoporous electrodes represent promising materials for numerous applications, including the immobilization of biomolecules in biotechnology and biosensing. Therefore, the fundamental understanding and controllability of the surface state of the electrode is essential. To achieve a precise surface charge control, nanoporous gold (npAu) is modified with self-assembled monolayers (SAMs) of different lengths (3-mercaptopropionic acid (MPA) and 16-mercaptohexadecanoic acid (MHDA)). Cyclic voltammetry and impedance spectroscopy are used to determine the pzc. The most distinct pzc, and thus the most precise charge control, is found for the long-chain MHDA. Subsequently, the proton transfer reaction was investigated as a function of pH and scan rate. The observed protonation/deprotonation reaction was qualitatively well in line with the literature for planar gold electrodes, albeit the fraction of electrochemical controllable SAMs increased by a factor of 10 compared to planar electrodes indicating attractive application potential.