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An electrocatalytic material for the H2 evolution reaction (HER) in acidic aqueous solution has been prepared by electropolymerization of Co(ii) dibenzotetraaza[14] annulene (CoTAA). Chemical analysis by X-ray photoelectron spectroscopy (XPS) confirms that the structural integrity of the [Co(II)-N4] motif is preserved in the poly-CoTAA film. In acetate buffer solution at pH 4.6, an overpotential η = -0.57 V is required to attain a catalytic current density -ik = 1 mA cmgeom(-2). The faradaic efficiency of poly-CoTAA for the HER is 90% over a period of one hour of electrolysis, but there is a decrease of the apparent concentration of Co sites after prolonged H2 production, which we ascribe to partial demetallation of the poly-CoTAA film at negative potentials.

A cobalt complex with a tripyridine-diamine pentadentate ligand was found to be a highly active catalyst for electrochemical H2 production from neutral water, with an activity of 860 mol H2 (mol cat)(-1) h(-1) (cm(2) Hg)(-1) over 60 h CPE experiment at -1.25 V in a pH 7 phosphate buffer solution, without considerable deactivation.

The diiron hydrogenase model Fe(2)(bdt)(CO)(6) (1, bdt = benzenedithiolate) was dispersed in aqueous micellar solution prepared from sodium dodecyl sulfate (SDS). Aqueous solution of 1 showed no sign of decomposition when left in contact with air over a period of several days. Current-potential responses recorded at a dropping mercury electrode over pH 7-3 were consistent with reduction of freely diffusing species. Catalysis of proton reduction was observed at pH < 6 with current densities exceeding 0.5 mA cm(-2) at an acid-to-catalyst ratio of 17. Bulk electrolysis at -0.66 V vs. SHE of solution of 1 at pH 3 confirmed the production of hydrogen with a Faradaic efficiency close to 100%. A mechanism involving initial reduction of 1 and subsequent proton-coupled electron transfer is proposed.

Despite its importance for understanding the behaviour of antimony in the environment, the oxidation kinetics of Sb(III) with natural oxidants is still not well understood. We have studied the oxidation of Sb(III) by hydrogen peroxide on a time scale of hours in the presence of some trace metals, Cu(II), Mn(II), Zn(II) and Pb(II), under pH and concentration conditions close to natural ones. The effects that these trace metals have on Sb(iii) oxidation by hydrogen peroxide vary. Zn(II) had no catalytic effect at all, but Cu(II), Mn(II) and Pb(II) did, though their effects were not uniform. Cu(II) significantly accelerated the reaction, which remained first-order with respect to Sb(III) at any Cu(II) concentration tested. Pb(II) and Mn(II) also enhanced the reaction rates, but the apparent order of the reaction with respect to Sb(III) changed to two. The trace metal effect observed was concentration dependent for Pb(II). The addition of the hydroxyl radical scavenger 2-propanol suggests that the trace metal catalytic effect observed involves the action of hydroxyl radicals, but that they are not responsible for the oxidation of Sb(III) by H2O2 in the absence of trace metals. The fact that Sb(III) can be oxidized by hydroxyl radicals present in water, even if it is not capable of producing them, has important environmental implications because hydroxyl radicals are known to be abundant in many natural waters such as seawater, humic-rich surface waters or rainwater.