Observation of oxygen evolution over a {Ni12}-cluster-based metal-organic framework

Abstract The development of efficient electrocatalysts based on non-noble metals for oxygen evolution reaction (OER) remains an important and challenging task. Multinuclear transition-metal clusters with high structural stability are promising OER catalysts but their catalytic role is poorly understood. Here we report the crystallographic observation of OER activity over robust {Ni 12 }-clusters immobilised in a porous metal-organic framework, NKU-100, by single-crystal X-ray diffraction as a function of external applied potential. We observed the aggregation of confined oxygen species around the {Ni 12 }-cluster as a function of applied potential during the electrocatalytic process. The refined occupancy of these oxygen species shows a strong correlation with the variation of current density. This study demonstrates that the enrichment of oxygen species in the secondary co-ordination sphere of multinuclear transition-metal clusters can promote the OER activity.