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Herein, a series of FeOx-MoP@MWCNT composite electrocatalysts was designed and prepared to investigate the influence of the content of FeOx on the water splitting performance. The optimized FeOx-MoP@MWCNTs-2 exhibits excellent hydrogen and oxygen evolution reaction activity while a cell voltage of 1.51 V with outstanding stability is attained, attributed to the synergistic effect of each component, as evidenced by the experimental and density functional theory results. The observed electrocatalytic activity outperforms current state-of-the