Efficient water electrolysis for hydrogen production constitutes a key segment for the upcoming hydrogen economy, but has been impeded by the lack of high-performance and low-cost electrocatalysts for, ideally, simultaneously expediting the kinetics of both hydrogen and oxygen evolution reactions (HER and OER). In this study, the favored binding energetics of OER and HER reaction intermediates on iron-doped nickel phosphides are first predicted by density functional theory (DFT) simulations, and then experimentally verified through the fabrication of Fe-doped Ni2P nanoparticles embedded in carbon nanotubes using metal–organic framework (MOF) arrays on nickel foam as the structural template. Systematic investigations on the effect of phosphorization and Fe doping reveal that while the former endows a larger benefit on OER than on HER, the latter enables not only modulating the electronic structure, but also tuning the micromorphology of the catalyst, synergistically leading to both enhanced HER and OER. As a result, extraordinary performances of constant water electrolysis are demonstrated requiring only a cell voltage of 1.66 V to afford a current density of 500 mA cm–2, far outperforming the benchmark electrode couple composed of Pt/C and RuO2. Postelectrolysis characterizations combined with DFT inspection further reveal that while the Fe-doped Ni2P species are mostly retained after prolonged HER, they are in situ converted to Fe/P-doped γ-NiOOH during OER, serving as the actual OER active sites with high activity.

Nanoframes of cobalt–iron bimetal phosphide enhance both HER and OER activities towards efficient overall water splitting.

Reversible oxygen conversion is important for various green energy technologies. Herein we synthesize a series of bimetallic coordination polymers by varying the Ni/Co ratio and using HITP (HITP=2,3,6,7,10,11‐hexaiminotriphenylene) as the ligand, to interrogate the role of metal centres in modulating the activity of the oxygen reduction reaction (ORR). Co3HITP2 and Ni3HITP2 are compared. Unpaired 3d electrons in Co3HITP2 result in less coplanarity but more radical character. Thus, despite of a reduced crystallinity and conductivity, the best ORR activity, comparable to 20 % Pt/C, is obtained for Co3HITP2, showing the 3d orbital configuration of the metal centre promotes ORR. Experimental and DFT studies show a transition of ORR pathway from four‐electron for Co3HITP2 to two‐electron for Ni3HITP2. Rechargeable zinc–air batteries using Co3HITP2 as the air cathode catalyst demonstrate excellent energy efficiency and stability.

Scheme 1. Schematic illustration of the fabrication process of h-CoFeNi LDHs through MOF-mediated topotactic transformation.

High efficiency overall water splitting enabled by a hierarchical Ni–C structure derived from 2D MOF sheets without heteroatom doping.