Nicolae Spataru

A study of RuO2 as an electrocatalyst for hydrogen evolution in alkaline solution

The hydrogen evolution reaction (HER) on RuO2 coated nickel electrodes was investigated by d.c. polarization studies and a.c. impedance measurements in alkaline solution. The electroactive RuO2 coatings were prepared by thermal decomposition of a RuCl3 solution at 450°C in air. The real surface area of the cathodes was estimated from cyclic voltammetric measurements and from the double layer capacitance (evaluated by impedance measurements). A mechanism for the HER has been proposed involving two steps (Volmer and Heyrovsky reactions). The rate constants of the forward and backward reactions of these two steps have been estimated by a nonlinear fitting procedure.

Particularities of photocatalysis and formation of reactive oxygen species on insulators and semiconductors: cases of SiO2, TiO2 and their composite SiO2-TiO2

Highly defected tubular SiO2 is found to outperform the activity of TiO2-P25 and the SiO2–TiO2 composite in photocatalytic H2 generation from methanol–water solution under simulated solar light AM 1.5. The enhanced performances of SiO2 come from the particularities of the reaction mechanism and ROS (reactive oxygen species) generation. The SiO2 exposed to light generates solely 1O2 (singlet oxygen). The TiO2-P25 produces uniquely large quantities of ˙OH radicals whereas the formation of O2− is evidenced only over SiO2–TiO2, along with small amounts of ˙OH. The TiO2 works as a photocatalyst by intermediation of ˙OH radicals. In contrast, the organic substrate is activated on the surface of SiO2 by the intra-band gap, isolated, surface quantum defects. Distinct reaction mechanisms, involving the participation of photogenerated charges and ROS, are proposed. The material-related ROS production can be of great practical importance in fields such as biology (germ inactivation), medicine (photodynamic therapy by 1O2), and synthesis of oxygenated organic compounds of great added value.