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Mechanistic Parameters of Electrocatalytic Water Oxidation on LiMn2 O4 in Comparison to Natural Photosynthesis.

ABSTRACT: Targeted improvement of the low efficiency of water oxidation during the oxygen evolution reaction (OER) is severely hindered by insufficient knowledge of the electrocatalytic mechanism on heterogeneous surfaces. We chose LiMn2 O4 as a model system for mechanistic investigations as it shares the cubane structure with the active site of photosystem?II and the valence of Mn3.5+ with the dark-stable S1 state in the mechanism of natural photosynthesis. The investigated LiMn2 O4 nanoparticles are electrochemically stable in NaOH electrolytes and show respectable activity in any of the main metrics. At low overpotential, the key mechanistic parameters of Tafel slope, Nernst slope, and reaction order have constant values on the RHE scale of 62(1)?mV?dec-1 , 1(1)?mV?pH-1 , -0.04(2), respectively. These values are interpreted in the context of the well-studied mechanism of natural photosynthesis. The uncovered difference in the reaction sequence is important for the design of efficient bio-inspired electrocatalysts.

SUBMITTER: Kohler L

PROVIDER: S-EPMC5725680 | biostudies-literature | 2017 Nov

REPOSITORIES: biostudies-literature

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Mechanistic Parameters of Electrocatalytic Water Oxidation on LiMn2 O4 in Comparison to Natural Photosynthesis.

Köhler Lennart L Ebrahimizadeh Abrishami Majid M Roddatis Vladimir V Geppert Janis J Risch Marcel M

ChemSusChem 20171027 22

Targeted improvement of the low efficiency of water oxidation during the oxygen evolution reaction (OER) is severely hindered by insufficient knowledge of the electrocatalytic mechanism on heterogeneous surfaces. We chose LiMn2 O4 as a model system for mechanistic investigations as it shares the cubane structure with the active site of photosystem II and the valence of Mn3.5+ with the dark-stable S1 state in the mechanism of natural photosynthesis. The investigat ...[more]

PMID: 28921902

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Project description:In this paper, we combine broken symmetry density functional calculations and electron paramagnetic resonance analysis to obtain the electronic structure of the penultimate S3 state of nature's water-oxidizing complex and determine the electronic pathway of O-O bond formation. Analysis of the electronic structure changes along the reaction path shows that two spin crossovers, facilitated by the geometry and magnetism of the water-oxidizing complex, are used to provide a unique low-energy pathway. The pathway is facilitated via the formation and stabilization of the [O2]3- ion. This ion is formed between ligated deprotonated substrate waters, O5 and O6, and is stabilized by antiferromagnetic interaction with the Mn ions of the complex. Combining the computational, crystallographic, and spectroscopic data, we show that an equilibrium exists between the O5 oxo and O6 hydroxo forms with an S = 3 spin state and a deprotonated O6 form containing a two-center one-electron bond in [O5O6]3- which we identify as the form detected using crystallography. This form corresponds to an S = 6 spin state which we demonstrate gives rise to a low-intensity EPR spectrum compared with the accompanying S = 3 state, making its detection via EPR difficult and overshadowed by the S = 3 form. Simulations using 70% of the S = 6 component give rise to a superior fit to the experimental W-band EPR spectral envelope compared with an S = 3 only form. Analyses of the most recent X-ray emission spectroscopy first moment changes for solution and time-resolved crystal data are also shown to support the model. The computational, crystallographic, and spectroscopic data are shown to coalesce to the same picture of a predominant S = 6 species containing the first one-electron oxidation product of two water molecules, that is, [O5O6]3-. Progression of this form to the two-electron-oxidized peroxo and three-electron-oxidized superoxo forms, leading eventually to the evolution of triplet O2, is proposed to be the pathway nature adopts to oxidize water. The study reveals the key electronic, magnetic, and structural design features of nature's catalyst which facilitates water oxidation to O2 under ambient conditions.

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Mechanistic Parameters of Electrocatalytic Water Oxidation on LiMn2 O4 in Comparison to Natural Photosynthesis.

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Mechanistic Parameters of Electrocatalytic Water Oxidation on LiMn<sub>2</sub> O<sub>4</sub> in Comparison to Natural Photosynthesis.

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