Marek Mooste

Electrochemical properties of gold and glassy carbon electrodes electrografted with an anthraquinone diazonium compound using the rotating disc electrode method

In this paper, gold and glassy carbon (GC) electrodes were electrochemically grafted with anthraquinone (AQ) groups derived from Fast Red AL salt via electrochemical reduction of AQ diazonium cations. For the first time, the electrografting was performed by combining the cyclic voltammetry (CV) or potential step method with the rotating disc electrode (RDE) technique in order to prepare thick films of AQ on Au and GC electrodes. For comparison purposes, a CV or potential step method without the RDE was also used. The attachment of thick AQ films to the Au electrode surface was confirmed by X-ray photoelectron spectroscopy and atomic force microscopy. The highest surface concentration value (ΓAQ) of AQ on the Au and GC electrodes (ca. 2.1 × 10−8 and 1.8 × 10−8 mol cm−2, respectively) was obtained by employing the combination of CV and RDE methods during the electrografting procedure. The oxygen reduction reaction results revealed that the electrochemical behaviour of AQ-modified Au electrodes does not depend on the ΓAQ value similar to the GC electrodes modified with thick AQ films. However, some differences were observed when the blocking effect of thick AQ films on Au and GC electrodes towards the ferri/ferrocyanide redox probe was studied.

Electrocatalysis of oxygen reduction on glassy carbon electrodes modified with anthraquinone moieties

Anthraquinone groups were electrochemically grafted to glassy carbon (GC) electrodes via methylene linker to study the oxygen reduction reaction (ORR) in alkaline medium. Two different anthraquinone derivatives, 2-bromomethyl-anthraquinone or 2-chloromethyl-anthraquinone, were used to modify the GC electrode surface. Several modification conditions encompassing potential cycling and electrolysis at a fixed potential were employed in order to vary the surface concentration of MAQ groups (ΓMAQ) and to study the dependence of the O2 reduction behaviour on electrografting procedure. Cyclic voltammetry confirmed the presence of anthraquinone moieties attached to the GC electrode and ΓMAQ varied in the range of (0.5–2.4) × 10−10 mol cm−2. Oxygen reduction was studied on MAQ-modified GC electrodes of various surface coverage using the rotating disc electrode (RDE) and rotating ring-disc electrode (RRDE) methods. The RDE and RRDE results of O2 reduction reveal that GC/MAQ electrodes show rather similar electrocatalytic behaviour towards the ORR yielding hydrogen peroxide as the final product.

Oxygen Reduction on Catalysts Prepared by Pyrolysis of Electrospun Styrene–Acrylonitrile Copolymer and Multi-walled Carbon Nanotube Composite Fibres

For the first time, the oxygen reduction reaction (ORR) is studied on pyrolysed electrospun multi-walled carbon nanotube (MWCNT) and styrene–acrylonitrile (SAN) composite fibre catalysts in alkaline medium. Scanning electron microscopy images revealed that the prepared catalysts mainly consist of MWCNTs, while nitrogen doping of the catalysts is confirmed by X-ray photoelectron spectroscopy. This indicates that SAN can be used as a nitrogen precursor. The ORR studies carried out by rotating disc electrode (RDE) and rotating ring-disc electrode (RRDE) methods showed that the prepared catalysts were considerably more active towards the ORR than the pristine MWCNTs.Graphical Abstract