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• S, C co-doped FeNiCeP/NF is prepared via high-valence metal engineering strategy. • High-valence Ce promotes electron transfer of metal phosphides. • The optimized material presents efficient OER, HER and supercapacitor performance. • The self-powered OWS is successfully assembled to produce hydrogen. The construction of cost-effective and high-performance metal organic framework (MOF) derived metal phosphides as multifunctional electrode materials for self-powered overall water splitting (OWS) is considerable promising. Herein, the trimetallic phosphides embedded in sulfur-containing carbon matrix (SC-FeNiCeP/NF) derived from high-valence metal engineered MOF are grown on nickel foam by hydrothermal and chemical vapor deposition for achieving self-powered OWS. Based on the electron coupling between the metal phosphide interface by high-valent Ce as "electronic storage" to accelerate electron transfer, the SC-FeNiCeP/NF as electrocatalysts present low overpotential with 208 mV and 107 mV at 10 mA cm−2 in oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively. For supercapacitor, the SC-FeNiCeP/NF nanoarray exhibits high specific capacitance with 2290 F g−1 at 1 A g−1. Combined with excellent SC-FeNiCeP/NF-based asymmetric supercapacitor (ASC) and OWS devices, the self-powered OWS are assembled to produce H 2 and O 2 simultaneously in alkaline water for up to ∼ 120 s, creating new possibilities for the energy storage and conversion systems based on the designable and multifunctional MOF-derived materials. [ABSTRACT FROM AUTHOR]

• The unique nanoarchitecture with PBA-derived nanocubes anchored on nanowires and nanoflakes are rationally constructed. • The proper P incorporation in (Ni,Co)Se 2 could greatly increase the electrochemical properties. • The operating potential of hybrid supercapacitor could be extended to 1.8 V. • The P-(Ni,Co)Se 2 //ZC device shows a high energy density of 45.0Wh kg−1 at the power density of 446.3 W kg−1. Nanostructure construction and composition tuning are two effective methods to accelerate electrochemical reaction kinetics and increase electroactive sites of nickel cobalt selenides nanoarrays. Herein, we have successfully designed and fabricated the P-(Ni,Co)Se 2 nanoarrays on activated carbon cloth with PBAs nanocubes anchored on the nanoflakes-nanowires by a facile hydrothermal method, followed precipitate reaction and phosphorization/selenylation treatment. The continuous hollow PBAs nanocubes and proper P incorporation in (Ni,Co)Se 2 could greatly increase active surface area and enhance the ions diffusion and charge transfer. The resultant P-(Ni,Co)Se 2 NAs electrode delivers a high areal capacity of 3.02C cm−2 (a specific capacity of 755C g−1) at 2 mA cm−2 and a good rate capability (2.61C cm−2 at 30 mA cm−2). Furthermore, the all-solid-state hybrid supercapacitor device is also constructed by using P-(Ni,Co)Se 2 NAs and ZIF-8 derived carbon as positive electrode and negative electrode, respectively, which shows a high energy density of 45.0 Wh kg−1 at the power density of 446.3 W kg−1. This work offers new strategies to synthesize transition nickel cobalt selenides for high performance supercapacitor devices. [ABSTRACT FROM AUTHOR]