The influencing factors on heterogeneous water oxidation catalysis (WOC) were investigated in a synthetic photosystem II model developed by adsorbing [(OH2)(terpy)MnIII(μ-O)2MnIV(terpy)(OH2)]3+ (terpy = 2,2′:6′,2″-terpyridine) (1) as an oxygen evolving center onto mica. For chemical WOC using a Ce4+ oxidant, the catalytic activity of 1 on mica increased by a factor of 2.3 or 1.4 by co-adsorption (0.015 mmol g−1) of redox-inactive trications of Al3+ or Ce3+ with 1 (0.15 mmol g−1), respectively, whereas it decreased by co-adsorption (0.25 mmol g−1) of excess Al3+ or Ce3+. The cooperative catalysis by two equivalents of the adsorbed 1 for water oxidation could be facilitated by enrichment of 1 by trications at their low co-adsorption conditions. The decreased catalytic activity at high trications co-adsorption conditions could be explained by impeded penetration of Ce4+ oxidant ions into a mica interlayer. For photochemical WOC containing a [Ru(bpy)3]2+ (bpy = 2,2′-bipyridine) photoexcitation center in mica, the drying treatment at 65 °C under the vacuum after 1 adsorption was required in adsorbate preparation, possibly to maintain favorable arrangement of 1 and [Ru(bpy)3]2+ in a mica interlayer. The drying treatment at 65 °C under the vacuum after [Ru(bpy)3]2+ adsorption inactivated the photochemical WOC. The proton-coupled electron transport from interior [Ru(bpy)3]2+ centers to ones near the surface in mica is considered to be suppressed by the drying treatment, which could be responsible for the inactivated photochemical WOC.
Research on Chemical Intermediates – Springer Journals
Published: Oct 15, 2014
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