A hydrated amorphous iron oxide nanoparticle as active water oxidation catalyst

Abstract

Developing efficient water oxidation catalysts (WOCs) with earth-abundant elements still remains a challenging task for artificial photosynthesis. Iron-based WOC is a promising candidate because it is economically cheap, little toxic and environmentally friendly. In this study, we found that the catalytic water oxidation activity on amorphous iron-based oxide/hydroxide (FeOx) can be decreased by an order of magnitude after the dehydration process at room temperature. Thermogravimetric analysis, XRD and Raman results indicated that the dehydration process of FeOx at room temperature causes the almost completely loss of water molecule with no bulk structural changes. Based on this finding, we prepared hydrated ultrasmall (ca. 2.2 nm) FeOx nanoparticles of amorphous feature, which turns out to be extremely active as WOC with turnover frequency (TOF) up to 9.3 s−1 in the photocatalytic Ru(bpy)32+-Na2S2O8 system. Our findings suggest that future design of active iron-based oxides as WOCs requires the consideration of their hydration status.