Dataset Information

Exceptional electrocatalytic oxygen evolution via tunable charge transfer interactions in La0.5Sr1.5Ni1-xFexO4±? Ruddlesden-Popper oxides.

ABSTRACT: The electrolysis of water is of global importance to store renewable energy and the methodical design of next-generation oxygen evolution catalysts requires a greater understanding of the structural and electronic contributions that give rise to increased activities. Herein, we report a series of Ruddlesden-Popper La0.5Sr1.5Ni1-xFexO4±? oxides that promote charge transfer via cross-gap hybridization to enhance electrocatalytic water splitting. Using selective substitution of lanthanum with strontium and nickel with iron to tune the extent to which transition metal and oxygen valence bands hybridize, we demonstrate remarkable catalytic activity of 10?mA?cm-2 at a 360?mV overpotential and mass activity of 1930 mA?mg-1ox at 1.63?V via a mechanism that utilizes lattice oxygen. This work demonstrates that Ruddlesden-Popper materials can be utilized as active catalysts for oxygen evolution through rational design of structural and electronic configurations that are unattainable in many other crystalline metal oxide phases.

SUBMITTER: Forslund RP

PROVIDER: S-EPMC6082882 | biostudies-other | 2018 Aug

REPOSITORIES: biostudies-other

ACCESS DATA

Publications

Exceptional electrocatalytic oxygen evolution via tunable charge transfer interactions in La0.5Sr1.5Ni1-xFexO4±δ Ruddlesden-Popper oxides.

Forslund Robin P RP Hardin William G WG Rong Xi X Abakumov Artem M AM Filimonov Dmitry D Alexander Caleb T CT Mefford J Tyler JT Iyer Hrishikesh H Kolpak Alexie M AM Johnston Keith P KP Stevenson Keith J KJ

Nature communications 20180808 1

The electrolysis of water is of global importance to store renewable energy and the methodical design of next-generation oxygen evolution catalysts requires a greater understanding of the structural and electronic contributions that give rise to increased activities. Herein, we report a series of Ruddlesden-Popper La0.5Sr1.5Ni1-xFexO4±δ oxides that promote charge transfer via cross-gap hybridization to enhance electrocatalytic water splittin ...[more]

PMID: 30089833

Similar Datasets

Project description:Compositionally versatile, nonstoichiometric, mixed ionic-electronic conducting metal oxides of the form A n+1B n O3n+1 (n = 1 → ∞; A = rare-earth-/alkaline-earth-metal cation; B = transition-metal (TM) cation) remain a highly attractive class of electrocatalysts for catalyzing the energy-intensive oxygen evolution reaction (OER). The current design strategies for describing their OER activities are largely derived assuming a static, unchanged view of their surfaces, despite reports of dynamic structural changes to 3d TM-based perovskites during OER. Herein, through variations in the A- and B-site compositions of A n+1B n O3n+1 oxides (n = 1 (A2BO4) or n = ∞ (ABO3); A = La, Sr, Ca; B = Mn, Fe, Co, Ni), we show that, in the absence of electrolyte impurities, surface restructuring is universally the source of high OER activity in these oxides and is dependent on the initial oxide composition. Oxide surface restructuring is induced by irreversible A-site cation dissolution, resulting in in situ formation of a TM oxyhydroxide shell on top of the parent oxide core that serves as the active surface for OER. The rate of surface restructuring is found to depend on (i) composition of A-site cations, with alkaline-earth-metal cations dominating lanthanide cation dissolution, (ii) oxide crystal phase, with n = 1 A2BO4 oxides exhibiting higher rates of A-site dissolution in comparison to n = ∞ ABO3 perovskites, (iii) lattice strain in the oxide induced by mixed rare-earth- and alkaline-earth-metal cations in the A-site, and (iv) oxide reducibility. Among the in situ generated 3d TM oxyhydroxide structures from A n+1B n O3n+1 oxides, Co-based structures are characterized by superior OER activity and stability, even in comparison to as-synthesized Co-oxyhydroxide, pointing to the generation of high active surface area structures through oxide restructuring. These insights are critical toward the development of revised design criteria to include surface dynamics for effectively describing the OER activity of nonstoichiometric mixed-metal oxides.

Dataset Information

Exceptional electrocatalytic oxygen evolution via tunable charge transfer interactions in La0.5Sr1.5Ni1-xFexO4±? Ruddlesden-Popper oxides.

Publications

Exceptional electrocatalytic oxygen evolution via tunable charge transfer interactions in La<sub>0.5</sub>Sr<sub>1.5</sub>Ni<sub>1-x</sub>Fe<sub>x</sub>O<sub>4±δ</sub> Ruddlesden-Popper oxides.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets