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Enhanced Photochemical Hydrogen Production by a Molecular Diiron Catalyst Incorporated into a Metal-Organic Framework
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.
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2013 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 135, no 45, 16997-17003 p.Article in journal (Refereed) Published
Abstract [en]

A molecular proton reduction catalyst [FeFe](dcbdt)(CO)(6) (1, dcbdt = 1,4-dicarboxylbenzene-2,3-dithiolate) with structural similarities to [FeFe]-hydrogenase active sites has been incorporated into a highly robust Zr(IV)-based metal-organic framework (MOF) by postsynthetic exchange (PSE). The PSE protocol is crucial as direct solvothermal synthesis fails to produce the functionalized MOF. The molecular integrity of the organometallic site within the MOF is demonstrated by a variety of techniques, including X-ray absorption spectroscopy. In conjunction with [Ru(bpy)(3)](2+) as a photosensitizer and ascorbate as an electron donor, MOF-[FeFe](dcbdt)(CO)(6) catalyzes photochemical hydrogen evolution in water at pH 5. The immobilized catalyst shows substantially improved initial rates and overall hydrogen production when compared to a reference system of complex 1 in solution. Improved catalytic performance is ascribed to structural stabilization of the complex when incorporated in the MOF as well as the protection of reduced catalysts 1(-) and 1(2-) from undesirable charge recombination with oxidized ascorbate.

Place, publisher, year, edition, pages
2013. Vol. 135, no 45, 16997-17003 p.
National Category
Natural Sciences
Identifiers
URN: urn:nbn:se:uu:diva-212862DOI: 10.1021/ja407176pISI: 000327103600042OAI: oai:DiVA.org:uu-212862DiVA: diva2:680096
Available from: 2013-12-17 Created: 2013-12-16 Last updated: 2017-12-06Bibliographically approved
In thesis
1. Mimicking the Outer Coordination Sphere in [FeFe]-Hydrogenase Active Site Models: From Extended Ligand Design to Metal-Organic Frameworks
Open this publication in new window or tab >>Mimicking the Outer Coordination Sphere in [FeFe]-Hydrogenase Active Site Models: From Extended Ligand Design to Metal-Organic Frameworks
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Biomimetic catalysis is an important research field, as a better understanding of nature´s powerful toolbox for the conversion of molecules can lead to technological progress. [FeFe]-hydrogenases are very efficient catalysts for hydrogen production. These enzymes play a crucial role in the metabolism of green algae and certain cyanobacteria. Their active site consists of a diiron complex that is embedded in an interactive protein matrix.

In this thesis, two pathways for mimicking the outer coordination sphere effects resulting from the protein matrix are explored.

The first is the construction of model complexes containing phosphine ligands that are coordinated to the iron center as well as covalently linked to the bridging ligand of the complex. The effect of such linkers is an increased energy barrier for the rotation of the Fe(CO2)(PL3)-subunit, which potentially could stabilize a terminal hydride that is an important intermediate in the proton reduction cycle.

The second pathway follows the incorporation of [FeFe]-hydrogenase active site model complexes into metal-organic frameworks (MOFs). Resulting MOF-catalysts exhibit increased photocatalytic activity compared to homogenous references due to a stabilizing effect on catalytic intermediates by the surrounding framework. Catalyst accessibility within the MOF and the influence of the framework on chemical reactivity are examined in the work presented. Furthermore, an initial step towards application of MOF-catalysts in a device was made by interfacing them with electrodes.

The work of this thesis highlights strategies for the improvement of biomimetic model catalysts and the knowledge gained can be transferred to other systems mimicking the function of enzymes. 

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2017. 115 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1498
Keyword
[FeFe]-hydrogenases, outer coordination sphere, model complexes, biomimetic catalysis, artificial photosynthesis, metal-organic frameworks
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-318975 (URN)978-91-554-9878-8 (ISBN)
Public defence
2017-05-19, Häggsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 13:15 (English)
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Supervisors
Available from: 2017-04-28 Created: 2017-03-30 Last updated: 2017-05-05

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Pullen, SonjaOrthaber, AndreasOtt, Sascha

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