4.6 Article

Hydroxyl-Decorated Diiron Complex as a [FeFe]-Hydrogenase Active Site Model Complex: Light-Driven Photocatalytic Activity and Heterogenization on Ethylene-Bridged Periodic Mesoporous Organosilica

Journal

CATALYSTS
Volume 12, Issue 3, Pages -

Publisher

MDPI
DOI: 10.3390/catal12030254

Keywords

[FeFe]-hydrogenase; periodic mesoporous organosilica; biomimetic chemistry; artificial photosynthesis; light-driven hydrogen evolution

Funding

  1. Ramon Areces Foundation [RAMON ARECES 16]
  2. Spanish Ministry of Science, Innovation and Universities (MICIU, FPU teaching and research fellowship) [FPU17/03981, RTI2018-101611-B-I00]
  3. Olle Engkvist Foundation [200-0523]
  4. Swedish Research Council [2015-04640]
  5. Swedish Research Council [2015-04640] Funding Source: Swedish Research Council

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A biomimetic model complex for light-driven hydrogen production was synthesized and anchored on heterogeneous supports, showing promising catalytic activity. The molecular complex achieved a decent turnover number, while the heterogenized complexes had slightly lower activities.
A biomimetic model complex of the [FeFe]-hydrogenase active site (FeFeOH) with an ethylene bridge and a pendant hydroxyl group has been synthesized, characterized and evaluated as catalyst for the light-driven hydrogen production. The interaction of the hydroxyl group present in the complex with 3-isocyanopropyltriethoxysilane provided a carbamate triethoxysilane bearing a diiron dithiolate complex (NCOFeFe), thus becoming a potentially promising candidate for anchoring on heterogeneous supports. As a proof of concept, the NCOFeFe precursor was anchored by a grafting procedure into a periodic mesoporous organosilica with ethane bridges (EthanePMO@NCOFeFe). Both molecular and heterogenized complexes were tested as catalysts for light-driven hydrogen generation in aqueous solutions. The photocatalytic conditions were optimized for the homogenous complex by varying the reaction time, pH, amount of the catalyst or photosensitizer, photon flux, and the type of light source (light-emitting diode (LED) and Xe lamp). It was shown that the molecular FeFeOH diiron complex achieved a decent turnover number (TON) of 70 after 6 h, while NCOFeFe and EthanePMO@NCOFeFe had slightly lower activities showing TONs of 37 and 5 at 6 h, respectively.

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