Hydrogenase-catalysed deposition of vivianite on mild steel

A simple device was designed with two mild steel electrodes placed face to face in the same phosphate solution and coupled through an external electrical circuit. A dialysis membrane retained hydrogenase from Ralstonia eutropha in contact with one electrode only. The simultaneous measurements of the electron flux in the electrical circuit and of nicotinamide adenine dinucleotide (NADH) production catalysed by hydrogenase proved that the enzyme induced the occurrence of cathodic and anodic micro-sites on the same electrode surface. A clear galvanic current was observed, which stopped after a few hours, because of the formation of a protective film of vivianite on the electrode that was in contact with hydrogenase. Hydrogenase in phosphate solution proved to be an effective trigger of mild steel corrosion. These results may be the basis of a new and easy-to-handle hydrogenase-catalysed phosphating process, which operates under mild conditions, avoids using toxic compounds, and is quite rapid.     

Platinum/vivianite bifunction catalysts for DMFC

Bi-functional catalysts are used to solve the poisoning problem caused by carbon monoxide (CO) which is the intermediate of direct methanol fuel cells (DMFCs). Flower-like vivianite (Fe₃(PO₄)₂·8H₂O) spheres with diameter around 10 μm are originally used as supports of Pt to form bifunction catalysts. The cyclic voltammetry in 1 M H₂SO₄ indicates that the electrochemical surface area (ECSA) of Pt reduced on as-prepared vivianite (Pt/Vi) was 105, greater than 91 m² g⁻¹ for the commercial Pt/C. Besides, Pt/Vi reveals the less CO poisoning effects, including the greater mass activity in methanol oxidation and the lower onset potential in CO-stripping than Pt/C. These excellent performances on electrolyzes are related to the chemical state of Fe³⁺ and the coexistence of Pt⁰ and Pt²⁺ in Pt/Vi. The former activates the water and yields Fe-OH_ads at lower potential and the latter may offer an easy way of electron transition.