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Analysis of the Active Species Responsible for Water Oxidation Using a Pentanuclear Fe Complex.

ABSTRACT: Water splitting with sunlight is today one of the most promising strategies that can be used to start the imperatively needed transition from fossil to solar fuels. To achieve this, one of the key reactions that need to be mastered is the electrocatalytic oxidation of water to dioxygen. Great developments have been achieved using transition metal complexes mainly based on Ru, but for technological applications it is highly desirable to be able to use earth-abundant transition metals. The intrinsic chemistry of first row transition metals and in particular the lability of their M-L bonds in water imposes serious challenges for the latter to work as real molecular catalysts. The present work addresses this issue based on a molecular pentanuclear Fe₅ complex and describes the different protocols and tests that need to be carried out in order to identify the real active species, responsible for the generation of dioxygen.

SUBMITTER: Pelosin P

PROVIDER: S-EPMC7398968 | biostudies-literature | 2020 Aug

REPOSITORIES: biostudies-literature

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Analysis of the Active Species Responsible for Water Oxidation Using a Pentanuclear Fe Complex.

Pelosin Primavera P Gil-Sepulcre Marcos M Garrido-Barros Pablo P Moonshiram Dooshaye D Benet-Buchholz Jordi J Gimbert-Suriñach Carolina C Llobet Antoni A

iScience 20200718 8

Water splitting with sunlight is today one of the most promising strategies that can be used to start the imperatively needed transition from fossil to solar fuels. To achieve this, one of the key reactions that need to be mastered is the electrocatalytic oxidation of water to dioxygen. Great developments have been achieved using transition metal complexes mainly based on Ru, but for technological applications it is highly desirable to be able to use earth-abundant transition metals. The intrins ...[more]

PMID: 32745986

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Project description:Photoelectrochemical water splitting can produce green hydrogen for industrial use and CO2-neutral transportation, ensuring the transition from fossil fuels to green, renewable energy sources. The iron-based electrocatalyst [FeII4FeIII(μ-3-O)(μ-L)6]3+ (LH = 3,5-bis(2-pyridyl)pyrazole) (1), discovered in 2016, is one of the fastest molecular water oxidation catalysts (WOC) based on earth-abundant elements. However, its water oxidation reaction mechanism has not been yet fully elucidated. Here, we present in situ X-ray spectroscopy and electron paramagnetic resonance (EPR) analysis of electrochemical water oxidation reaction (WOR) promoted by (1) in water-acetonitrile solution. We observed transient reactive intermediates during the in situ electrochemical WOR, consistent with a coordination sphere expansion prior to the onset of catalytic current. At a pre-catalytic (~+1.1 V vs. Ag/AgCl) potential, the distinct g~2.0 EPR signal assigned to FeIII/FeIV interaction was observed. Prolonged bulk electrolysis at catalytic (~+1.6 V vs. Ag/AgCl) potential leads to the further oxidation of Fe centers in (1). At the steady state achieved with such electrolysis, the formation of hypervalent FeV=O and FeIV=O catalytic intermediates was inferred with XANES and EXAFS fitting, detecting a short Fe=O bond at ~1.6 Å. (1) was embedded into MIL-126 MOF with the formation of (1)-MIL-126 composite. The latter was tested in photoelectrochemical WOR and demonstrated an improvement of electrocatalytic current upon visible light irradiation in acidic (pH=2) water solution. The presented spectroscopic analysis gives further insight into the catalytic pathways of multinuclear systems and should help the subsequent development of more energy- and cost-effective catalysts of water splitting based on earth-abundant metals. Photoelectrocatalytic activity of (1)-MIL-126 confirms the possibility of creating an assembly of (1) inside a solid support and boosting it with solar irradiation towards industrial applications of the catalyst.

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Analysis of the Active Species Responsible for Water Oxidation Using a Pentanuclear Fe Complex.

Publications

Analysis of the Active Species Responsible for Water Oxidation Using a Pentanuclear Fe Complex.

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