Electrocatalytic Oxidation of Alcohols Tripropylamine and DNA with Ligand-Free Gold Nanoclusters on Nitrided Carbon

摘要

Electrocatalytic properties of ligand-free gold nanoclusters (AuNCs, <2 nm) grown on nitrided carbon supports (denoted as AuNCs@N-C) were evaluated for the oxidation of representative organic molecules including alcohols, an amine, and deoxyguanosine in oligonucleotides. AuNCs@N-C catalysts were incorporated into films of architecture {PDDA/AuNCs@N-C}n by using layer-by-layer assembly with oppositely charged poly(diallyldimethylammonium) (PDDA) on pyrolytic graphite (PG) electrodes. Cyclic voltammetry and electrochemical impedance spectroscopy (EIS) were used to survey the electrocatalytic properties of these AuNCs@N-C films. Ligand-free AuNCs in these films demonstrated excellent electrocatalytic oxidation activity with maximum peak currents and the lowest potentials for oxidizing ethanol, propanol, and tripropylamine (TprA) compared to controls with Au-surface capping agents or to larger sized Au nanocrystals on the nitrided carbon supports. EIS kinetic studies showed that ligand-free AuNCs films have the smallest charge-transfer resistance, largest electrochemically active surface area, and largest apparent standard rate constants, as compared to the control films for all compounds examined. DNA films on AuNCs@N-C were oxidized at deoxyguanosine moieties with good catalytic activity that depended on charge transport within the films.