Mechanistic Investigations of Water Oxidation by a Molecular Cobalt Oxide Analogue: Evidence for a Highly Oxidized Intermediate and Exclusive Terminal Oxo Participation.

Artificial photosynthesis (AP) promises to replace society's dependence on fossil energy resources via conversion of sunlight into sustainable, carbon-neutral fuels. However, large-scale AP implementation remains impeded by a dearth of cheap, efficient catalysts for the oxygen evolution reaction (OER). Cobalt oxide materials can catalyze the OER and are potentially scalable due to the abundance of cobalt in the Earth's crust; unfortunately, the activity of these materials is insufficient for practical AP implementation.

Photon-initiated homolysis of peroxynitrous acid.

Laser flash photolysis of ONOOH at 355 nm and a pH of 4.0-5.5 causes homolysis of ONOOH nearly exclusively at the N-O bond rather than at the O-O bond (HO(2)(*)/HO(*) > 25:1).

Preparation and properties of lithium and sodium peroxynitrite.

We describe the preparation of aqueous solutions of LiONOO and NaONOO from (Me4N)ONOO. An aqueous solution of analytically pure, commercially available (Me4N)ONOO is applied to an Amberlyst 15 column at 4 degrees C, and the Me4N+ is rapidly (in 20 min) exchanged against Li+ or Na+. The exchanged peroxynitrite is produced in yields of ca.