Enlarging the Ni–O Bond Polarizability in a Phosphorene-Hosted Metal–Organic Framework for Boosted Water Oxidation Electrocatalysis

The emerging lattice-oxygen oxidation mechanism (LOM) presents attractive opportunities for breaking the scaling relationship to boost oxygen evolution reaction (OER) with the direct OLattice–*O interaction. However, currently the LOM-triggering rationales are still debated, and a streamlined physicochemical paradigm is extremely desirable for the design of LOM-defined OER catalysts. Herein, a Ni metal–organic framework/black phosphorene (NiMOF/BP) heterostructure is theoretically profiled and constructed as a catalytic platform for the LOM-derived OER studies. It is found that the p-type BP host can enlarge the Ni–O bond polarizability of NiMOF through the Ni–O bond stretching and Ni valence declining synergically. Such an enlarged bond polarizability will in principle alleviate the lattice oxygen confinement to benefit the LOM pathway and OER performance. As a result, the optimized NiMOF/BP catalyst exhibits promising OER performance with a low overpotential of 260 mV at 10 mA cm–2 and long-term stability in 1 M KOH electrolyte. Both experiment and calculation results suggest the activated LOM pathway with a more balanced step barrier in the NiMOF/BP OER catalyst. This research puts forward Ni–O bond polarizability as the criterion to design LOM-scaled electrocatalysts for water oxidation.