Remolding the reactivity of metal active sites is critical to facilitate renewable electricity-powered water electrolysis. Doping heteroatoms, such as Se, into a metal crystal lattice has been considered an effective approach, yet usually suffers from loss of functional heteroatoms during harsh electrocatalytic conditions, thus leading to the gradual inactivation of the catalysts. Here, we report a new heteroatom-containing molecule-enhanced strategy toward sustainable oxygen evolution improvement. An organoselenium ligand, bis(3,5-dimethyl-1H-pyrazol-4yl)selenide containing robust C−Se−C covalent bonds equipped in the precatalyst of ultrathin metal−organic nanosheets Co-SeMON, is revealed to significantly enhance the catalytic mass activity of the cobalt site by 25 times, as well as extend the catalyst operation time in alkaline conditions by 1 or 2 orders of magnitude compared with these reported metal selenides. A combination of various in situ/ex situ spectroscopic techniques, ab initio molecular dynamics, and density functional theory calculations unveiled the organoselenium intensified mechanism, in which the nonclassical bonding of Se to O-containing intermediates endows adsorption-energy regulation beyond the conventional scaling relationship. Our results showcase the great potential of moleculeenhanced catalysts for highly efficient and economical water oxidation.

Remodeling the active surface through fabricating heterostructures can substantially enhance alkaline water electrolysis driven by renewable electrical energy. However, there are still great challenges in the synthesis of highly reactive and robust heterostructures to achieve both ampere-level current density hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, we report a new Co/CeO2 heterojunction self-supported electrode for sustainable overall water splitting. The self-supporting Co/CeO2 heterostructures required only low overpotentials of 31.9 ± 2.2, 253.3 ± 2.7, and 316.7 ± 3 mV for HER and 214.1 ± 1.4, 362.3 ± 1.9, and 400.3 ± 3.7 mV for OER at 0.01, 0.5, and 1.0 A·cm–2, respectively, being one of the best Co-based bifunctional electrodes. Electrolyzer constructed from this electrode acting as an anode and cathode merely required cell voltages of 1.92 ± 0.02 V at 1.0 A·cm–2 for overall water splitting. Multiple characterization techniques combined with density functional theory calculations disclosed the different active sites on the anode and cathode, and the charge redistributions on the heterointerfaces that can optimize the adsorption of H and oxygen-containing intermediates, respectively. This study presents the tremendous prospective of self-supporting heterostructures for effective and economical overall water splitting.