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The two-dimensional layered double hydroxides (LDHs) and zero-dimensional metal clusters have emerged as promising nanomaterials in the field of sustainable water oxidation, which can also facilitate joint experimental and computational studies. In this study, the synthesis of Ni6@LDH composites, comprising atomically precise Ni6(MPA)12 (MPA: mercaptopropionic acid) clusters embedded into LDH nanosheets via electrostatic interaction, represents a significant advancement in the development of nanomaterials for sustainable water oxidation. Ni6@NiFe-LDH exhibits superior electrochemical performance in oxygen evolution reaction (OER), exhibiting OER overpotentials of 198 mV@10 mA·cm−2 and 290 mV@100 mA·cm−2 with a low Tafel slope of 29 mV·dec−1. It surpasses the corresponding NiFe-LDH and commercial RuO2 catalysts, primarily due to the synergistic interaction between Ni6 clusters and LDHs. Interestingly, our combined experimental and computational approach reveals that the M-OOHads formation is the rate-determining step (RDS) for the Ni6-based catalysts, differing from the RDS for NiFe-LDH itself (the M-Oads formation). These efforts serve as an attempt to push forward the current research frontier to study structure–property relationships progressing from the micro-/nano-level to the precise atomic-level.
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